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  • 1.
    Denisova, Aleksandra
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
    Expanding the (Cross-)Hyperconjugation of 1,4-Disilacyclohexa-2,5-dienes to Larger Monomers and Oligomers: A Computational Investigation2016In: RSC Advances, E-ISSN 2046-2069, Vol. 6, no 43, p. 36961-36970Article in journal (Refereed)
    Abstract [en]

    We used density functional theory calculations to examine molecules that can be regarded as expanded 1,4-disilacyclohexa-2,5-dienes as well as oligomers based on these or 1,4-disilacyclohexa-2,5-diene with the aim to identify systems with extended (cross-)hyperconjugation. Among the three "expanded 1,4-disilacyclohexa-2,5-dienes" considered cyclobutadisilole is the most interesting as it has a higher thermodynamic stability than the isomeric 1,6-disilacyclodeca-2,3,4,7,8,9-hexaene and significantly lower first electronic excitation energy than 1,6-disilacyclodeca-2,4,7,9-tetraene. Cyclobutadisilole with trimethylsilyl substituents at Si shows particularly low excitations with the first strong transition at 3.46 eV (358 nm), i.e., similar to 1.1 eV lower than in 1,4-disilacyclohexa-2,5-diene. The monomers were connected into oligomers via their Si atoms using bis(dimethylsilanediyl) linkers, and some extended hyperconjugation was revealed. The first allowed UV/Vis excitation in the cyclobutadisilole-based tetramers is calculated at 2.57 eV (482 nm), although the lowering in excitation energies when going from monomer to tetramer is merely similar to 0.5 eV and hyperconjugation has modest impact on geometries. Yet, the tetra(cyclobutadisilole) has a significantly lower first allowed excitation when compared to a previously studied tetra(1,4-disilacyclohexadiene) with first excitation at 3.9 eV (318 nm).

  • 2.
    Denisova V, Aleksandra
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
    Tibbelin, Julius
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
    A Computational Investigation of the Substituent Effects on Geometric, Electronic, and Optical Properties of Siloles and 1,4-Disilacyclohexa-2,5-dienes2017In: Molecules, ISSN 1431-5157, E-ISSN 1420-3049, Vol. 22, no 3, article id 370Article in journal (Refereed)
    Abstract [en]

    Thirty two differently substituted siloles 1a–1p and 1,4-disilacyclohexa-2,5-dienes 2a–2p were investigated by quantum chemical calculations using the PBE0 hybrid density functional theory (DFT) method. The substituents included σ-electron donating and withdrawing, as well as π-electron donating and withdrawing groups, and their effects when placed at the Si atom(s) or at the C atoms were examined. Focus was placed on geometries, frontier orbital energies and the energies of the first allowed electronic excitations. We analyzed the variation in energies between the orbitals which correspond to HOMO and LUMO for the two parent species, here represented as ΔεHL, motivated by the fact that the first allowed transitions involve excitation between these orbitals. Even though ΔεHL and the excitation energies are lower for siloles than for 1,4-disilacyclohexa-2,5-dienes the latter display significantly larger variations with substitution. The ΔεHL of the siloles vary within 4.57–5.35 eV (ΔΔεHL = 0.78 eV) while for the 1,4-disilacyclohexa-2,5-dienes the range is 5.49–7.15 eV (ΔΔεHL = 1.66 eV). The excitation energy of the first allowed transitions display a moderate variation for siloles (3.60–4.41 eV) whereas the variation for 1,4-disilacyclohexa-2,5-dienes is nearly doubled (4.69–6.21 eV). Cyclobutadisiloles combine the characteristics of siloles and 1,4-disilacyclohexa-2,5-diene by having even lower excitation energies than siloles yet also extensive variation in excitation energies to substitution of 1,4-disilacyclohexa-2,5-dienes (3.47–4.77 eV, variation of 1.30 eV).

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  • 3.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Conjugation in Organic Group 14 Element Compounds: Design, Synthesis and Experimental Evaluation2014Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    This thesis focuses on the chemical concept of conjugation, i.e., electron delocalization, and the effect it has on electronic and optical properties of molecules. The emphasis is on electron delocalization across a saturated σ-bonded segment, and in our studies these segments are either inserted between π-conjugated moieties or joined together to form longer chains. The electronic and optical properties of these compounds are probed and compared to those of traditionally π-conjugated compounds. The investigations utilize a combination of qualitative chemical bonding theories, quantum chemical calculations, chemical syntheses and different spectroscopic methods.

    Herein, it is revealed that a saturated σ-bonded segment inserted between two π-systems can have optical and electronic properties similar to a cross-conjugated compound when substituents with heavy Group 14 elements (Si, Ge or Sn) are attached to the central atom. We coined the terminology cross-hyperconjugation for this interaction, and have shown it by both computational and spectroscopic means. This similarity is also found in cyclic compounds, for example in the 1,4-disilacyclohexa-2,5-dienes, as we reveal that there is a cyclic aspect of cross-hyperconjugation. Cross-hyperconjugation can further also be found in smaller rings such as siloles and cyclopentadienes, and we show on the similarities between these and their cross-π-conjugated analogues, the fulvenes. Here, this concept is combined with that of excited state aromaticity and the electronic properties of these systems are rationalized in terms of “aromatic chameleon” effects. We show that the optical properties of these systems can be rationally tuned and predicted through the choice of substituents and knowledge about the aromaticity rules in both ground and excited states.

    We computationally examine the relation between conjugation and conductance and reveal that oligomers of 1,4-disilacyclohexa-2,5-dienes and related analogues can display molecular cord properties. The conductance through several σ-conjugated silicon compounds were also examined and show that mixed silicon and carbon bicyclo[2.2.2]octane compounds do not provide significant benefits over the open-chain oligosilanes. However, cyclohexasilanes, a synthetic precursor to the bicyclic compounds, displayed conformer-dependent electronic structure variations that were not seen for cyclohexanes. This allowed for computational design of a mechanically activated conductance switch.

    List of papers
    1. Cross-hyperconjugation: An unexplored orbital interaction between pi-conjugated and saturated molecular segments
    Open this publication in new window or tab >>Cross-hyperconjugation: An unexplored orbital interaction between pi-conjugated and saturated molecular segments
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    2013 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 52, no 3, p. 983-987Article in journal (Refereed) Published
    Abstract [en]

    Crossing a barrier: Molecules with saturated ER2 units (E=C or Si, R=electron-releasing group) inserted between two π-conjugated segments have electronic and optical properties that resemble those of cross-conjugated molecules (see figure). This cross-hyperconjugation provides a deeper understanding of the conjugation phenomenon, and is an alternative to cross-conjugation in the design of molecules for nano and materials applications.

    Keywords
    conjugation, cross-conjugation, Group 14 elements, hyperconjugation, optical tuning
    National Category
    Natural Sciences
    Identifiers
    urn:nbn:se:uu:diva-194990 (URN)10.1002/anie.201206030 (DOI)000313688100036 ()
    Available from: 2013-02-21 Created: 2013-02-20 Last updated: 2017-12-06Bibliographically approved
    2. Charge transfer through cross-hyperconjugated versus cross-pi-conjugated bridges: an intervalence charge transfer study
    Open this publication in new window or tab >>Charge transfer through cross-hyperconjugated versus cross-pi-conjugated bridges: an intervalence charge transfer study
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    2013 (English)In: Chemical Science, ISSN 2041-6520, Vol. 4, no 9, p. 3522-3532Article in journal (Refereed) Published
    Abstract [en]

    Recently there has been much interest in electron transfer and transport through cross-conjugated molecules as interesting test cases for the interplay between molecular and electronic structure as well as potential motifs in the design of new compounds for molecular electronics. Herein we expand on this concept and present the synthesis and characterization of a series of four organic mixed-valence dyads to probe the effect of the bridge structure on the electronic coupling. The electronic coupling between two triarylamine units could be mediated either by cross-hyperconjugation through a saturated ER2 bridge (E = C or Si, R = alkyl or silyl group), or via a cross-conjugated pi-system. The aim of the study is to compare the electron transfer through the various saturated bridges to that of a cross-pi-conjugated bridge. The electronic coupling in these mixed-valence compounds was determined by analysis of intervalence charge transfer bands, and was found to be in the range of 100-400 cm(-1). A complementary DFT and TD-DFT study indicated that the electronic coupling in the dyads with saturated ER2 segments is highly conformer dependant. Furthermore, the calculations showed that two types of interactions contribute to the electronic coupling; a through-bond cross-(hyper)conjugation mechanism and a through-space mechanism. Taken together, these findings suggest the possibility for new architectures for molecular electronics applications utilizing cross-hyperconjugation through properly selected saturated segments which have comparable electron transfer characteristics as regular cross-pi-conjugated molecules.

    National Category
    Natural Sciences
    Identifiers
    urn:nbn:se:uu:diva-208680 (URN)10.1039/c3sc50844g (DOI)000322391800021 ()
    Available from: 2013-10-07 Created: 2013-10-07 Last updated: 2014-06-30Bibliographically approved
    3. 1,4-Disilacyclohexa-2,5-diene: a molecular building block that allows for remarkably strong neutral cyclic cross-hyperconjugation
    Open this publication in new window or tab >>1,4-Disilacyclohexa-2,5-diene: a molecular building block that allows for remarkably strong neutral cyclic cross-hyperconjugation
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    2014 (English)In: Chemical Science, ISSN 2041-6520, Vol. 5, no 1, p. 360-371Article in journal (Refereed) Published
    Abstract [en]

    2,3,5,6-Tetraethyl-1,4-disilacyclohexa-2,5-dienes with either four chloro (1a), methyl (1b), or trimethylsilyl (TMS) (1c) substituents at the two silicon atoms were examined in an effort to design rigid compounds with strong neutral cross-hyperconjugation between pi- and sigma-bonded molecular segments arranged into a cycle. Remarkable variations in the lowest electronic excitation energies, lowest ionization energies, and the first oxidation potentials were observed upon change of substituents, as determined by gas phase ultraviolet (UV) absorption spectroscopy, ultraviolet photoelectron spectroscopy (UPS), and cyclic voltammetry. A particularly strong neutral cyclic cross-hyperconjugation was observed in 1c. Its lowest electron binding energy (7.1 eV) is distinctly different from that of 1b (8.5 eV). Molecular orbital analysis reveals a stronger interaction between filled pi(C=C) and pi(SiR2) group orbitals in 1c than in 1a and 1b. The energy shift in the highest occupied molecular orbital is also reflected in the first oxidation potentials as observed in the cyclic voltammograms of the respective compounds (1.47, 0.88, and 0.46 V for 1a, 1b and 1c, respectively). Furthermore, 1,4-disilacyclohexadiene 1c absorbs strongly at 273 nm (4.55 eV), whereas 1a and 1b have no symmetry allowed excitations above 215 nm (below 5.77 eV). Thus, suitably substituted 1,4-disilacyclohexa-2,5-dienes could represent novel building blocks for the design of larger cross-hyperconjugated molecules as alternatives to traditional purely cross-p-conjugated analogues, and could allow for design of molecules with properties that are not accessible to those that are exclusively pi-conjugated.

    National Category
    Natural Sciences
    Identifiers
    urn:nbn:se:uu:diva-213891 (URN)10.1039/c3sc52389f (DOI)000327601600045 ()
    Available from: 2014-01-06 Created: 2014-01-05 Last updated: 2022-01-28Bibliographically approved
    4. Optimization of the Cyclic Cross-Hyperconjugation in 1,4-Ditetrelcyclohexa-2,5-dienes
    Open this publication in new window or tab >>Optimization of the Cyclic Cross-Hyperconjugation in 1,4-Ditetrelcyclohexa-2,5-dienes
    2014 (English)In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 33, no 12, p. 2997-3004Article in journal (Refereed) Published
    Abstract [en]

    Cyclic cross-hyperconjugation can exist to variable extents in 1,4-ditetrelcyclohexa-2,5-dienes, i.e., all-carbon cyclohexa-1,4-dienes and 1,4-disila/digerma/distanna/diplumbacyclohexa-2,5-dienes. In this study we first use density functional theory (DFT) computations to optimize the conjugation strength by seeking the optimal atom E and substituent group E'Me-3 in the two saturated E(E'Me-3)(2) moieties (E and E' as the same or different tetrel (group 14) elements). We reveal that the all-carbon cyclohexadienes with gradually heavier E'Me-3 substituents at the two saturated carbon atoms display significant cross-hyperconjugation. The first electronic excitations in these compounds, which formally have two isolated C=C bonds, are calculated to reach wavelengths as long as 400 nm (excitation energies of 3.1 eV). These transitions are mostly forbidden, and the lowest allowed transitions are found at 387 nm (3.2 eV). The silicon analogues are also cross-hyperconjugated, while a decline is observed in the 1,4-digerma/distanna/diplumbacyclohexa-2,5-diene. Experiments on two substituted 1,4-disilacyclohexa-2,5-dienes confirm the effect of the E'Me3 substituents, with regard to both electronic excitations and geometries as determined by UV absorption spectroscopy and X-ray crystallography, respectively. At the end, we reveal through computations how electron-donating and electron-withdrawing substituents at the C=C double bonds influence the electronic properties of the all-carbon ring. We find that the first calculated excitation, which is forbidden, can be shifted to 440 nm (2.83 eV). This shows to what extent cyclic cross-hyperconjugation can affect the electronic and optical properties of a compound with two formally isolated C=C double bonds.

    National Category
    Organic Chemistry
    Research subject
    Chemistry with specialization in Organic Chemistry
    Identifiers
    urn:nbn:se:uu:diva-221022 (URN)10.1021/om5001875 (DOI)000337936800008 ()
    Available from: 2014-03-24 Created: 2014-03-24 Last updated: 2017-12-12Bibliographically approved
    5. Using Ground and Excited State Aromaticity to Understand Cyclopentadiene and Silole Excitation Energies and Excited State Polarities
    Open this publication in new window or tab >>Using Ground and Excited State Aromaticity to Understand Cyclopentadiene and Silole Excitation Energies and Excited State Polarities
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    (English)Article in journal (Other academic) Submitted
    National Category
    Chemical Sciences
    Research subject
    Chemistry with specialization in Organic Chemistry
    Identifiers
    urn:nbn:se:uu:diva-221027 (URN)
    Available from: 2014-03-24 Created: 2014-03-24 Last updated: 2014-06-30Bibliographically approved
    6. In Search of Flexible Molecular Wires with Near Conformer-Independent Conjugation and Conductance: A Computational Study
    Open this publication in new window or tab >>In Search of Flexible Molecular Wires with Near Conformer-Independent Conjugation and Conductance: A Computational Study
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    2014 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 118, no 11, p. 5637-5649Article in journal (Refereed) Published
    Abstract [en]

    Oligomers of 1,4-disila/germa/stannacyclohexa-2,5-dienes as well as all-carbon 1,4-cyclohexadienes connected via E—E single bonds (E = C, Si, Ge, or Sn) were studied through quantum chemical calculations in an effort to identify conformationally flexible molecular wires that act as molecular “electrical cords” having conformer-independent conjugative and conductive properties. Our oligomers display neutral hyperconjugative interactions (σ/π-conjugation) between adjacent σ(E—E) and π(C═C) bond orbitals, and these interactions do not change with conformation. The energies and spatial distributions of the highest occupied molecular orbitals of methyl-, silyl-, and trimethylsilyl (TMS)-substituted 1,4-disilacyclohexa-2,5-diene dimers, and stable conformers of trimers and tetramers, remain rather constant upon Si–Si bond rotation. Yet, steric congestion may be a concern in some of the oligomer types. The calculated conductances for the Si-containing tetramers are similar to that of a σ-conjugated linear all-anti oligosilane (a hexadecasilane) with equally many bonds in the conjugated paths. Moreover, the Me-substituted 1,4-disilacyclohexadiene tetramer has modest conductance fluctuations with Si–Si bond rotations when the electrode–electrode distance is locked (variation by factor 30), while the fluctuations under similar conditions are larger for the analogous TMS-substituted tetramer. When the electrode–electrode distance is changed several oligomers display small conductance variations within certain distance intervals, e.g., the mean conductance of TMS-substituted 1,4-disilacyclohexa-2,5-diene tetramer is almost unchanged over 9 Å of electrode–electrode distances.

    Place, publisher, year, edition, pages
    American Chemical Society (ACS), 2014
    National Category
    Physical Chemistry
    Research subject
    Chemistry with specialization in Organic Chemistry
    Identifiers
    urn:nbn:se:uu:diva-209260 (URN)10.1021/jp409767r (DOI)000333381300003 ()
    Available from: 2013-10-16 Created: 2013-10-16 Last updated: 2017-12-06Bibliographically approved
    7. Coupling of Disilane and Trisilane Segments Through Zero, One, Two, and Three Disilanyl Bridges in Cyclic and Bicyclic Saturated Carbosilanes
    Open this publication in new window or tab >>Coupling of Disilane and Trisilane Segments Through Zero, One, Two, and Three Disilanyl Bridges in Cyclic and Bicyclic Saturated Carbosilanes
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    2013 (English)In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 32, no 2, p. 396-405Article in journal (Refereed) Published
    Abstract [en]

    Several six-membered cyclic and [2.2.2]bicyclic organo-silanes with varying proportions of silicon atoms in the bridges have been prepared following a stepwise approach that exploits dianionic polysilanes. Focus in our analysis was placed on the bicyclic compounds which all have silicon atoms at the bridgehead positions. Quantum chemical calculations of these compounds revealed the possibility to enhance the coupling through a single cisoid tetrasilane cage segment by replacing one or two of the other -SiMe2SiMe2- bridges with -CH2CH2- bridges. UV absorption spectroscopy revealed a red shift in the lowest visible transitions when going from a bicyclo[2.2.2]octane with three -SiMe2SiMe2- bridges to those with two or one such bridge. However, these red shifts are deceptive, as the lowest vertically excited singlet states, which are dark according to TD-DFT calculations, do not display the same trend. Still, since these compounds have (i) excellent structural rigidity, (ii) provide potentials for functionalization through their exocyclic trimethylsilyl groups, and (iii) display electronic structure variations with the number of -SiMe2SiMe2- bridges, they could be interesting for further studies: e.g., in single-molecule electronics.

    National Category
    Natural Sciences
    Identifiers
    urn:nbn:se:uu:diva-196040 (URN)10.1021/om3006678 (DOI)000314332100007 ()
    Available from: 2013-03-04 Created: 2013-03-04 Last updated: 2017-12-06Bibliographically approved
    8. Conductance through Carbosilane Cage Compounds: A Computational Investigation
    Open this publication in new window or tab >>Conductance through Carbosilane Cage Compounds: A Computational Investigation
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    2013 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 117, no 42, p. 21692-21699Article in journal (Refereed) Published
    Abstract [en]

    Silicon is still the dominating material in microelectronics, yet primarily π-conjugated hydrocarbons are investigated in the field of single-molecule electronics even though linear oligosilanes are σ-conjugated. A drawback with the latter is their high conformational flexibility which strongly affects conductance. Here we report on a first principles density functional theory investigation of a series of rigid [2.2.2]bicyclic carbosilanes with 3, 2, 1, or 0 disilanylene bridges, providing all-silicon paths for charge transport. It is explored if these paths can be seen as independent and equivalent current paths acting as parallel resistors. For high conductance through the carbosilanes they need to be anchored to the gold electrodes via groups that are matched with the σ-conjugated paths of the oligosilane cage segment, and we find that silyl (SiH3) groups are better matched than thiophenol groups. Even for the carbosilane with three disilanylene bridges we find that the most transmitting conductance channel is not equally distributed on the three parallel bridges. In addition, there is significant communication between the various pathways, which results in destructive interference lowering the conductance. Taken together, the different disilanylene bridges in the cage compounds do not act as parallel resistors.

    Keywords
    Molecular electronics, organosilicon chemistry, electronic structure, density functional theory, sigma conjugation
    National Category
    Physical Chemistry
    Identifiers
    urn:nbn:se:uu:diva-209236 (URN)10.1021/jp407485n (DOI)000326260000008 ()
    Available from: 2013-10-16 Created: 2013-10-15 Last updated: 2017-12-06Bibliographically approved
    9. Configuration- and Conformation-Dependent Electronic Structure Variations in 1,4-Disubstituted Cyclohexanes Enabled by a Carbon-to-Silicon Exchange
    Open this publication in new window or tab >>Configuration- and Conformation-Dependent Electronic Structure Variations in 1,4-Disubstituted Cyclohexanes Enabled by a Carbon-to-Silicon Exchange
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    2014 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 20, no 30, p. 9304-9311Article in journal (Other academic) Published
    Abstract [en]

    Cyclohexane, with its well-defined conformers, could be an ideal force-controlled molecular switch if it were to display substantial differences in electronic and optical properties between its conformers. We utilize sigma conjugation in heavier analogues of cyclohexanes (i.e. cyclohexasilanes) and show that 1,4-disubstituted cyclohexasilanes display configuration-and conformation-dependent variations in these properties. Cis- and trans-1,4-bis(trimethylsilylethynyl)-cyclohexasilanes display a 0.11 V difference in their oxidation potentials (computed 0.11 V) and a 0.34 eV difference in their lowest UV absorption (computed difference between first excitations 0.07 eV). This is in stark contrast to differences in the corresponding properties of analogous all-carbon cyclohexanes (computed 0.02 V and 0.03 eV, respectively). Moreover, the two chair conformers of the cyclohexasilane trans isomer display large differences in electronic-structure-related properties. This enables computational design of a mechanically force-controlled conductance switch with a calculated single-molecule ON/OFF ratio of 213 at zero-bias voltage.

    National Category
    Physical Chemistry
    Identifiers
    urn:nbn:se:uu:diva-209259 (URN)10.1002/chem.201402610 (DOI)000339568800023 ()
    Note

    De 2 sista författarna delar sistaförfattarskapet.

    Available from: 2013-10-16 Created: 2013-10-16 Last updated: 2017-12-06Bibliographically approved
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  • 4.
    Emanuelsson, Rikard
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Denisova, Aleksandra
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Baumgartner, Judith
    Institut für Chemie, Universität Graz.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Optimization of the Cyclic Cross-Hyperconjugation in 1,4-Ditetrelcyclohexa-2,5-dienes2014In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 33, no 12, p. 2997-3004Article in journal (Refereed)
    Abstract [en]

    Cyclic cross-hyperconjugation can exist to variable extents in 1,4-ditetrelcyclohexa-2,5-dienes, i.e., all-carbon cyclohexa-1,4-dienes and 1,4-disila/digerma/distanna/diplumbacyclohexa-2,5-dienes. In this study we first use density functional theory (DFT) computations to optimize the conjugation strength by seeking the optimal atom E and substituent group E'Me-3 in the two saturated E(E'Me-3)(2) moieties (E and E' as the same or different tetrel (group 14) elements). We reveal that the all-carbon cyclohexadienes with gradually heavier E'Me-3 substituents at the two saturated carbon atoms display significant cross-hyperconjugation. The first electronic excitations in these compounds, which formally have two isolated C=C bonds, are calculated to reach wavelengths as long as 400 nm (excitation energies of 3.1 eV). These transitions are mostly forbidden, and the lowest allowed transitions are found at 387 nm (3.2 eV). The silicon analogues are also cross-hyperconjugated, while a decline is observed in the 1,4-digerma/distanna/diplumbacyclohexa-2,5-diene. Experiments on two substituted 1,4-disilacyclohexa-2,5-dienes confirm the effect of the E'Me3 substituents, with regard to both electronic excitations and geometries as determined by UV absorption spectroscopy and X-ray crystallography, respectively. At the end, we reveal through computations how electron-donating and electron-withdrawing substituents at the C=C double bonds influence the electronic properties of the all-carbon ring. We find that the first calculated excitation, which is forbidden, can be shifted to 440 nm (2.83 eV). This shows to what extent cyclic cross-hyperconjugation can affect the electronic and optical properties of a compound with two formally isolated C=C double bonds.

  • 5.
    Emanuelsson, Rikard
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Hao
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Gogoll, Adolf
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Enthalpic versus Entropic Contribution to the Quinone Formal Potential in a Polypyrrole-Based Conducting Redox Polymer2016In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 38, p. 21178-21183Article in journal (Refereed)
    Abstract [en]

    A conducting redox polymer (CPR) based on pyrrole with a hydroquinone pendant group was synthesized through electropolymerization of the corresponding monomer. The formal potential (E-0') in aqueous solution at different pH as well as in MeCN containing equal amounts of pyridiniumtriflates and the corresponding free pyridine with different pK(a) was investigated. E-0' could be completely recovered in MeCN, and by utilizing pyridine bases with different donor acceptor strengths, a decrease of 61 meV/pK(a) was found that corresponded exactly to the pH dependence of E-0' in aqueous electrolyte. To separate the entropic and enthalpic contributions to E-0', temperature-dependent electrochemistry was performed. Two different modes of operation with changing pH/pK(a) between the two media were revealed. In MeCN, E-0' varies only because of the enthalpic contribution as the entropic contribution is unaffected by change in pKa. In water, there is primarily an entropic contribution to E-0' with changing pH due to solvation of the proton. The presented results are expected to open up for new design possibilities of CRPs based on ion coordinating redox groups for electrical energy storage.

  • 6.
    Emanuelsson, Rikard
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Karlsson, Christoffer
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Hao
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Kosgei, Cosmas Kipyego
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Quinone based conducting redox polymers for electrical energy storage2017In: Russian journal of electrochemistry, ISSN 1023-1935, E-ISSN 1608-3342, Vol. 53, no 1, p. 8-15Article in journal (Refereed)
    Abstract [en]

    Conducting redox polymers (CRPs) constitute a promising class of materials for the development of organic matter based batteries with the potential to overcome the main limitations connected to this type of rechargeable battery systems including low conductivity and dissolution problems. In this report we show that the potential of quinones can be effectively tuned into the conducting region of polypyrrole (PPy), both in water based solutions and in acetonitrile, which is a prerequisite for profitable combination of the two units. We also present a device where both anode and cathode are made from PPy substituted with different quinone pendant groups and where good rate performance is achieved without any conductivity additives thus providing support for the hypothesized synergetic effect of a conducting polymer backbone and a covalently attached redox active pendant group. This device constitutes, to the best of our knowledge, the first all-CRP based battery reported to date.

  • 7.
    Emanuelsson, Rikard
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Karlsson, Christoffer
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Hao
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Kosgei, Cosmas Kipyego
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Quinone based conducting redox polymers for electrical energy storage2017In: Elektrokhimiya, ISSN 0424-8570, Vol. 53, no 1, p. 11-20Article in journal (Refereed)
    Abstract [en]

    Conducting redox polymers (CRPs) constitute a promising class of materials for the development of organic matter based batteries with the potential to overcome the main limitations connected to this type of rechargeable battery systems including low conductivity and dissolution problems. In this report we show that the potential of quinones can be effectively tuned into the conducting region of polypyrrole (PPy), both in water based solutions and in acetonitrile, which is a prerequisite for profitable combination of the two units. We also present a device where both anode and cathode are made from PPy substituted with different quinone pendant groups and where good rate performance is achieved without any conductivity additives thus providing support for the hypothesized synergetic effect of a conducting polymer backbone and a covalently attached redox active pendant group. This device constitutes, to the best of our knowledge, the first all-CRP based battery reported to date.

  • 8.
    Emanuelsson, Rikard
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Löfås, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Wallner, Andreas
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry. Institut für Anorganische Chemie, Technische Universität Graz.
    Nauroozi, Djawed
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
    Baumgartner, Judith
    Institut für Anorganische Chemie, Technische Universität Graz.
    Marschner, Christoph
    Institut für Anorganische Chemie, Technische Universität Graz.
    Ahuja, Rajeev
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Ott, Sascha
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
    Grigoriev, Anton
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Configuration- and Conformation-Dependent Electronic Structure Variations in 1,4-Disubstituted Cyclohexanes Enabled by a Carbon-to-Silicon Exchange2014In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 20, no 30, p. 9304-9311Article in journal (Other academic)
    Abstract [en]

    Cyclohexane, with its well-defined conformers, could be an ideal force-controlled molecular switch if it were to display substantial differences in electronic and optical properties between its conformers. We utilize sigma conjugation in heavier analogues of cyclohexanes (i.e. cyclohexasilanes) and show that 1,4-disubstituted cyclohexasilanes display configuration-and conformation-dependent variations in these properties. Cis- and trans-1,4-bis(trimethylsilylethynyl)-cyclohexasilanes display a 0.11 V difference in their oxidation potentials (computed 0.11 V) and a 0.34 eV difference in their lowest UV absorption (computed difference between first excitations 0.07 eV). This is in stark contrast to differences in the corresponding properties of analogous all-carbon cyclohexanes (computed 0.02 V and 0.03 eV, respectively). Moreover, the two chair conformers of the cyclohexasilane trans isomer display large differences in electronic-structure-related properties. This enables computational design of a mechanically force-controlled conductance switch with a calculated single-molecule ON/OFF ratio of 213 at zero-bias voltage.

  • 9.
    Emanuelsson, Rikard
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Löfås, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Zhu, Jun
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry. State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University.
    Ahuja, Rajeev
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Grigoriev, Anton
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    In Search of Flexible Molecular Wires with Near Conformer-Independent Conjugation and Conductance: A Computational Study2014In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 118, no 11, p. 5637-5649Article in journal (Refereed)
    Abstract [en]

    Oligomers of 1,4-disila/germa/stannacyclohexa-2,5-dienes as well as all-carbon 1,4-cyclohexadienes connected via E—E single bonds (E = C, Si, Ge, or Sn) were studied through quantum chemical calculations in an effort to identify conformationally flexible molecular wires that act as molecular “electrical cords” having conformer-independent conjugative and conductive properties. Our oligomers display neutral hyperconjugative interactions (σ/π-conjugation) between adjacent σ(E—E) and π(C═C) bond orbitals, and these interactions do not change with conformation. The energies and spatial distributions of the highest occupied molecular orbitals of methyl-, silyl-, and trimethylsilyl (TMS)-substituted 1,4-disilacyclohexa-2,5-diene dimers, and stable conformers of trimers and tetramers, remain rather constant upon Si–Si bond rotation. Yet, steric congestion may be a concern in some of the oligomer types. The calculated conductances for the Si-containing tetramers are similar to that of a σ-conjugated linear all-anti oligosilane (a hexadecasilane) with equally many bonds in the conjugated paths. Moreover, the Me-substituted 1,4-disilacyclohexadiene tetramer has modest conductance fluctuations with Si–Si bond rotations when the electrode–electrode distance is locked (variation by factor 30), while the fluctuations under similar conditions are larger for the analogous TMS-substituted tetramer. When the electrode–electrode distance is changed several oligomers display small conductance variations within certain distance intervals, e.g., the mean conductance of TMS-substituted 1,4-disilacyclohexa-2,5-diene tetramer is almost unchanged over 9 Å of electrode–electrode distances.

  • 10.
    Emanuelsson, Rikard
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sterby, Mia
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    All-Organic Proton Batteries from Conducting Redox Polymers2017Conference paper (Refereed)
  • 11.
    Emanuelsson, Rikard
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sterby, Mia
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strømme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    An All-Organic Proton Battery2017In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 139, no 13, p. 4828-4834Article in journal (Refereed)
    Abstract [en]

    Rechargeable batteries that use organic matter as. the capacity-carrying material have previously been considered a technology for the future. Earlier batteries in which both the anode and cathode consisted of organic material required significant amounts of conductive additives and were often based on metal-ion electrolytes containing Li+ or Na+. However, we have used conducting poly(3,4-ethylenedioxythiophene) (PEDOT), functionalized with anthraquinone (PEDQT-AQ) or, benzonquinone (PEDOT-BQ) pendant groups as the negative and positive electrode materials, respectively, to make an all-organic proton battery devoid of metals. The electrolyte consists of a proton donor and acceptor slurry containing substituted pyridinium triflates and the corresponding pyridine base. This slurry allows the 2e(-)/2H(+) quinone/hydroquinone redox reactions while suppressing proton reduction in the battery cell. By using strong (acidic) proton donors, the formal potential of the quinone redox reactions is tuned into the potential region in which the PEDOT backbone is conductive, thus eliminating the need for conducting additives. In this all-organic proton battery cell, PEDOT-AQ and PEDOT-BQ deliver 103 and 120 mAh g(-1), which correspond to 78% and 75%, respectively, of the theoretical specific capacity of the materials at an average cell potential of 0.5 V. We show that PEDOT-BQ determines the cycling stability of the device while PEDOT-AQ provides excellent reversibility for at least 1000 cycles. This proof-of-concept shows the feasibility of assembling all organic proton batteries which require no conductive additives and also reveals where the challenges and opportunities lie on the path to producing plastic batteries.

  • 12.
    Emanuelsson, Rikard
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Tibbelin, Julius
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Wallner, Andreas
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Smith, Joshua R.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Strong neutral cross-hyperconjugation and linear hyperconjugation enabled by saturated Group 14 element E(E ' R-3)(2), (E ' R-3)E-E(E ' R-3), and E(E ' R-2)(2)E segments2013In: Abstracts of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 245, p. 1246-INOR-Article in journal (Other academic)
  • 13.
    Emanuelsson, Rikard
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Wallner, Andreas
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Ng, Eugene A. M.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Smith, J. R.
    Nauroozi, Djawed
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
    Ott, Sascha
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Cross-hyperconjugation: An unexplored orbital interaction between pi-conjugated and saturated molecular segments2013In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 52, no 3, p. 983-987Article in journal (Refereed)
    Abstract [en]

    Crossing a barrier: Molecules with saturated ER2 units (E=C or Si, R=electron-releasing group) inserted between two π-conjugated segments have electronic and optical properties that resemble those of cross-conjugated molecules (see figure). This cross-hyperconjugation provides a deeper understanding of the conjugation phenomenon, and is an alternative to cross-conjugation in the design of molecules for nano and materials applications.

  • 14.
    Gaiser, Philipp
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    Zaar, Felicia
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Surface immobilization of molecular catalysts using conducting redox polymers2022Conference paper (Refereed)
  • 15.
    Göransson, Erik
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Jorner, Kjell
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Markle, Todd F.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Hammarström, Leif
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Charge transfer through cross-hyperconjugated versus cross-pi-conjugated bridges: an intervalence charge transfer study2013In: Chemical Science, ISSN 2041-6520, Vol. 4, no 9, p. 3522-3532Article in journal (Refereed)
    Abstract [en]

    Recently there has been much interest in electron transfer and transport through cross-conjugated molecules as interesting test cases for the interplay between molecular and electronic structure as well as potential motifs in the design of new compounds for molecular electronics. Herein we expand on this concept and present the synthesis and characterization of a series of four organic mixed-valence dyads to probe the effect of the bridge structure on the electronic coupling. The electronic coupling between two triarylamine units could be mediated either by cross-hyperconjugation through a saturated ER2 bridge (E = C or Si, R = alkyl or silyl group), or via a cross-conjugated pi-system. The aim of the study is to compare the electron transfer through the various saturated bridges to that of a cross-pi-conjugated bridge. The electronic coupling in these mixed-valence compounds was determined by analysis of intervalence charge transfer bands, and was found to be in the range of 100-400 cm(-1). A complementary DFT and TD-DFT study indicated that the electronic coupling in the dyads with saturated ER2 segments is highly conformer dependant. Furthermore, the calculations showed that two types of interactions contribute to the electronic coupling; a through-bond cross-(hyper)conjugation mechanism and a through-space mechanism. Taken together, these findings suggest the possibility for new architectures for molecular electronics applications utilizing cross-hyperconjugation through properly selected saturated segments which have comparable electron transfer characteristics as regular cross-pi-conjugated molecules.

  • 16.
    Günther, Tyran
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Oka, Kouki
    Olsson, Sandra K.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    Åhlén, Michelle
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Tohnai, Norimitsu
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    Redox-site accessibility of composites containing a 2D redox-active covalent organic framework: from optimization to application2023In: Journal of Materials Chemistry A, ISSN 2050-7488, E-ISSN 2050-7496, Vol. 11, no 26, p. 13923-13931Article in journal (Refereed)
    Abstract [en]

    Redox-active covalent organic frameworks (RACOFs) can be employed in various functional materials and enesrgy applications. A crucial performance or efficiency indicator is the percentage of redox centres that can be utilised. Herein, the term redox-site accessibility (RSA) is defined and shown to be an effective metric for developing and optimising a 2D RACOF (viz., TpOMe-DAQ made from 2,4,6-trimethoxy-1,3,5-benzenetricarbaldehyde [TpOMe] and 2,6-diaminoanthraquinone [DAQ]) as an anode material for potential organic-battery applications. Pristine TpOMe-DAQ utilises only 0.76% of its redox sites, necessitating the use of conductivity-enhancement strategies such as blending it with different conductive carbons, or performing in situ polymerisation with EDOT (3,4-ethylenedioxythiophene) to form a conductive polymer. While conductive carbon-RACOF composites showed a modest RSA improvement of 4.0%, conductive polymer-RACOF composites boosted the redox-site usage (RSA) to 90% at low mass loadings. The material and electrochemical characteristics of the conductive polymer-RACOF composite containing more-than-necessary conductive polymer showed a reduced surface area but almost identical electrochemical behaviour, compared to the optimal ratio. The high RSA of the optimally loaded composite was replicated in a RACOF-air battery with over 90% active redox sites. We believe that the reported approach and methods, which can be employed on a milligram scale, could serve as a general guide for the electrification and characterisation of RACOFs, as well as for other redox-active porous polymers.

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  • 17.
    Huang, Hao
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sterby, Mia
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Quinone Based Conducting Redox Polymer for Energy Storage2017Conference paper (Refereed)
  • 18.
    Huang, Xiao
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    Yang, Li
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Bergquist, Jonas
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry, Analytical Chemistry.
    Strømme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Gogoll, Adolf
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    A versatile route to polythiophenes with functional pendant groups using alkyne chemistry2016In: Beilstein Journal of Organic Chemistry, ISSN 2195-951X, E-ISSN 1860-5397, Vol. 12, p. 2682-2688Article in journal (Refereed)
    Abstract [en]

    A new versatile polythiophene building block, 3-(3,4-ethylenedioxythiophene)prop-1-yne (pyEDOT) (3), is prepared from glycidol in four steps in 28% overall yield. pyEDOT features an ethynyl group on its ethylenedioxy bridge, allowing further functionalization by alkyne chemistry. Its usefulness is demonstrated by a series of functionalized polythiophene derivatives that were obtained by pre- and post-electropolymerization transformations, provided by the synthetic ease of the Sonogashira coupling and click chemistry.

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    fulltext
  • 19. Ivanko, Iryna
    et al.
    Lindfors, Tom
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Conjugated redox polymer with poly(3,4-ethylenedioxythiophene) backbone and hydroquinone pendant groups as the solid contact in potassium-selective electrodes2021In: Sensors and actuators. B, Chemical, ISSN 0925-4005, E-ISSN 1873-3077, Vol. 329, article id 129231Article in journal (Refereed)
    Abstract [en]

    We have used for the first time a conjugated redox polymer with hydroquinone (HQ) pendant groups covalently attached to the poly(3,4-ethylenedioxythiophene) (PEDOT) backbone as the solid contact (SC) in plasticized poly(vinyl chloride) (PVC) based K+-selective electrodes (K-SCISE). Redox couples are one of the simplest ways to precisely adjust the standard potential (E°) of the SCISEs, but usually the initially high E° reproducibility is lost quite quickly due to leaching out of non-covalently bound redox molecules from the SCISE. In PEDOT-HQ, the covalently attached HQ groups prevent the leaching and simultaneously allow additional charge storage in PEDOT-HQ that is ca. 25–30 times higher than for unsubstituted PEDOT. Before the ion-selective membrane (ISM) deposition, we controlled the potential of the SC with high reproducibility (±0.4 mV, n = 5) by pre-polarization in a mixture of acetonitrile containing potassium tetrakis(pentafluorophenyl)borate and perchloric acid as proton source. Pre-polarization of the SC close to the formal potential where the redox buffer capacity is highest gave the best potential reproducibility. However, after the ISM deposition, the K-SCISEs showed in the best case an E° reproducibility of ±2.8 mV (n = 5). Chronopotentiometric measurements reveal that only a minor fraction of the very high redox capacitance of PEDOT-HQ can be utilized for the ion-to-electron transduction beneath the ISM. The influence of this shortcoming on the E° reproducibility of the SCISEs has been underestimated for most SC materials. Modification of the commonly used PVC-ISM formulations to allow faster ion transfer at the SC/ISM interface could be one way of overcoming the disadvantage.

  • 20.
    Jorner, Kjell
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC. Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
    Dreos, Ambra
    Chalmers, Dept Chem & Chem Engn, Kemigarden 4, SE-41296 Gothenburg, Sweden..
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    El Bakouri, Ouissam
    Univ Girona, Dept Quim, IQCC, Campus Montilivi, Girona 17003, Spain..
    Fernández Galván, Ignacio
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry. Uppsala Univ, UC3, Box 523, SE-75120 Uppsala, Sweden..
    Borjesson, Karl
    Chalmers, Dept Chem & Chem Engn, Kemigarden 4, SE-41296 Gothenburg, Sweden.;Univ Gothenburg, Dept Chem & Mol Biol, Kemigarden 4, SE-41296 Gothenburg, Sweden..
    Feixas, Ferran
    Univ Girona, Dept Quim, IQCC, Campus Montilivi, Girona 17003, Spain..
    Lindh, Roland
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry. Uppsala Univ, UC3, Box 523, SE-75120 Uppsala, Sweden..
    Zietz, Burkhard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Moth-Poulsen, Kasper
    Chalmers, Dept Chem & Chem Engn, Kemigarden 4, SE-41296 Gothenburg, Sweden..
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics. Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Unraveling factors leading to efficient norbornadiene-quadricyclane molecular solar-thermal energy storage systems2017In: Journal of Materials Chemistry A, ISSN 2050-7488, Vol. 5, no 24, p. 12369-12378Article in journal (Refereed)
    Abstract [en]

    Developing norbornadiene-quadricyclane (NBD-QC) systems for molecular solar-thermal (MOST) energy storage is often a process of trial and error. By studying a series of norbornadienes (NBD-R-2) doubly substituted at the C7-position with R = H, Me, and iPr, we untangle the interrelated factors affecting MOST performance through a combination of experiment and theory. Increasing the steric bulk along the NBD-R-2 series gave higher quantum yields, slightly red-shifted absorptions, and longer thermal lifetimes of the energy-rich QC isomer. However, these advantages are counterbalanced by lower energy storage capacities, and overall R = Me appears most promising for short-term MOST applications. Computationally we find that it is the destabilization of the NBD isomer over the QC isomer with increasing steric bulk that is responsible for most of the observed trends and we can also predict the relative quantum yields by characterizing the S-1/S-0 conical intersections. The significantly increased thermal half-life of NBD-iPr(2) is caused by a higher activation entropy, highlighting a novel strategy to improve thermal half-lives of MOST compounds and other photo-switchable molecules without affecting their electronic properties. The potential of the NBD-R-2 compounds in devices is also explored, demonstrating a solar energy storage efficiency of up to 0.2%. Finally, we show how the insights gained in this study can be used to identify strategies to improve already existing NBD-QC systems.

  • 21.
    Jorner, Kjell
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Ayub, Rabia
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Denisova, Aleksandra
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Siloles and cyclopentadienes as "aromatic chameleons" influenced by aromaticity in both the ground state and lowest electronically excited states2014In: Abstracts of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 247, article id 560-ORGNArticle in journal (Other academic)
  • 22.
    Jorner, Kjell
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Dahlstrand, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Tong, Hui
    Denisova, Aleksandra V.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Impact of Ground- and Excited-State Aromaticity on Cyclopentadiene and Silole Excitation Energies and Excited-State Polarities2014In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 20, no 30, p. 9295-9303Article in journal (Refereed)
    Abstract [en]

    A new qualitative model for estimating the properties of substituted cyclopentadienes and siloles in their lowest pi pi* excited states is introduced and confirmed through quantum chemical calculations, and then applied to explain earlier reported experimental excitation energies. According to our model, which is based on excited-state aromaticity and antiaromaticity, siloles and cyclopentadienes are cross-hyperconjugated "aromatic chameleons" that adapt their electronic structures to conform to the various aromaticity rules in different electronic states (Huckel's rule in the pi(2) electronic ground state (S-0) and Baird's rule in the lowest pi pi* excited singlet and triplet states (S-1 and T-1)). By using pen-and-paper arguments, one can explain polarity changes upon excitation of substituted cyclopentadienes and siloles, and one can tune their lowest excitation energies by combined considerations of ground-and excited-state aromaticity/antiaromaticity effects. Finally, the "aromatic chameleon" model can be extended to other monocyclic compound classes of potential use in organic electronics, thereby providing a unified view of the S-0, T-1, and S-1 states of a range of different cyclic cross-pi-conjugated and cross-hyperconjugated compound classes.

  • 23.
    Jorner, Kjell
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Dahlstrand, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Tong, Hui
    State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences.
    Densiova, Aleksandra
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Using Ground and Excited State Aromaticity to Understand Cyclopentadiene and Silole Excitation Energies and Excited State PolaritiesArticle in journal (Other academic)
  • 24.
    Löfgren, Rebecka
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Quinone based conducting redox polymer on carbon substrate as electrode material for energy storage2021In: SweGRIDS 10th conference / [ed] SweGRIDS, Solna, 2021, Vol. 10Conference paper (Refereed)
  • 25.
    Löfgren, Rebecka
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Kouki, O.
    Organic Quinone based Conducting Redox Polymers for Sustainable and Green Energy Storage2022In: European Materials Research Society conference 2022 / [ed] European Materials Research Society, Warsava: European Materials Research Society , 2022Conference paper (Refereed)
  • 26.
    Löfås, Henrik
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Ahuja, Rajeev
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Grigoriev, Anton
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Conductance through Carbosilane Cage Compounds: A Computational Investigation2013In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 117, no 42, p. 21692-21699Article in journal (Refereed)
    Abstract [en]

    Silicon is still the dominating material in microelectronics, yet primarily π-conjugated hydrocarbons are investigated in the field of single-molecule electronics even though linear oligosilanes are σ-conjugated. A drawback with the latter is their high conformational flexibility which strongly affects conductance. Here we report on a first principles density functional theory investigation of a series of rigid [2.2.2]bicyclic carbosilanes with 3, 2, 1, or 0 disilanylene bridges, providing all-silicon paths for charge transport. It is explored if these paths can be seen as independent and equivalent current paths acting as parallel resistors. For high conductance through the carbosilanes they need to be anchored to the gold electrodes via groups that are matched with the σ-conjugated paths of the oligosilane cage segment, and we find that silyl (SiH3) groups are better matched than thiophenol groups. Even for the carbosilane with three disilanylene bridges we find that the most transmitting conductance channel is not equally distributed on the three parallel bridges. In addition, there is significant communication between the various pathways, which results in destructive interference lowering the conductance. Taken together, the different disilanylene bridges in the cage compounds do not act as parallel resistors.

  • 27.
    Löfås, Henrik
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Jahn, B. O.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Wärnå, John
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Ahuja, Rajeev
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Grigoriev, Anton
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    A computational study of potential molecular switches that exploit Baird's rule on excited-state aromaticity and antiaromaticity2014In: Faraday discussions, ISSN 1359-6640, E-ISSN 1364-5498, Vol. 174, p. 105-124Article in journal (Refereed)
    Abstract [en]

    A series of tentative single-molecule conductance switches which could be triggered by light were examined by computational means using density functional theory (DFT) with non-equilibrium Green's functions (NEGF). The switches exploit the reversal in electron counting rules for aromaticity and antiaromaticity upon excitation from the electronic ground state (S0) to the lowest [small pi][small pi]* excited singlet and triplet states (S1 or T1), as described by Huckel's and Baird's rules, respectively. Four different switches and one antifuse were designed which rely on various photoreactions that either lead from the OFF to the ON states (switches 1, 2 and 4, and antifuse 5) or from the ON to the OFF state (switch 3). The highest and lowest ideal calculated switching ratios are 1175 and 5, respectively, observed for switches 1 and 4. Increased thermal stability of the 1-ON isomer is achieved by benzannulation (switch 1B-OFF/ON). The effects of constrained electrode-electrode distances on activation energies for thermal hydrogen back-transfer from 1-ON to 1-OFF and the relative energies of 1-ON and 1-OFF at constrained geometries were also studied. The switching ratio is strongly distance-dependent as revealed for 1B-ON/OFF where it equals 711 and 148 when the ON and OFF isomers are calculated in electrode gaps with distances confined to either that of the OFF isomer or to that of the ON isomer, respectively.

  • 28.
    Oka, Kouki
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials. Waseda Univ, Dept Appl Chem, Shinjuku Ku, 3-4-1 Okubo, Tokyo 1658555, Japan.;Waseda Univ, Res Inst Sci & Engn, Shinjuku Ku, 3-4-1 Okubo, Tokyo 1658555, Japan..
    Löfgren, Rebecka
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Nishide, Hiroyuki
    Waseda Univ, Dept Appl Chem, Shinjuku Ku, 3-4-1 Okubo, Tokyo 1658555, Japan.;Waseda Univ, Res Inst Sci & Engn, Shinjuku Ku, 3-4-1 Okubo, Tokyo 1658555, Japan..
    Oyaizu, Kenichi
    Waseda Univ, Dept Appl Chem, Shinjuku Ku, 3-4-1 Okubo, Tokyo 1658555, Japan.;Waseda Univ, Res Inst Sci & Engn, Shinjuku Ku, 3-4-1 Okubo, Tokyo 1658555, Japan..
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Conducting Redox Polymer as Organic Anode Material for Polymer-Manganese Secondary Batteries2020In: ChemElectroChem, E-ISSN 2196-0216, Vol. 7, no 15, p. 3336-3340Article in journal (Refereed)
    Abstract [en]

    Manganese-based aqueous batteries have attracted significant attention due to their earth-abundant components and low environmental burden. However, state-of-the-art manganese-zinc batteries are poorly rechargeable, owing to dendrite formation on the zinc anode. Organic materials could provide a safe and sustainable replacement. In the present work, a conducting redox polymer (CRP) based on a trimer of EPE (E=3,4-ethylenedioxythiophene; P=3,4-propylenedioxythiophene) and a naphthoquinone (NQ) pendant group is used as anode in polymer-manganese secondary batteries. The polymer shows stable redox conversion around+0.05 V vs. Ag/AgCl, and fast kinetics that involves proton cycling during pendant group redox conversion. For the first time, a CRP-manganese secondary battery was fabricated with pEP(NQ)E as the anode, manganese oxide as the cathode, and manganese-containing acidic aqueous solution as the electrolyte. This battery yielded a discharge voltage of 1.0 V and a discharging capacity of 76 mAh/g(anode)over >50 cycles and high rate capabilities (up to 10 C).

  • 29.
    Oka, Kouki
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials. Department of Applied Chemistry and Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 165-8555 Japan..
    Löfgren, Rebecka
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Nishide, Hiroyuki
    Department of Applied Chemistry and Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 165-8555 Japan..
    Oyaizu, Kenichi
    Department of Applied Chemistry and Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 165-8555 Japan..
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Conducting Redox Polymer as Organic Anode Material for Polymer-Manganese Secondary Batteries2020In: ChemElectroChem, E-ISSN 2196-0216, Vol. 7, no 15, p. 3336-3340Article in journal (Refereed)
    Abstract [en]

    Manganese-based aqueous batteries have attracted significant attention due to their earth-abundant components and low environmental burden. However, state-of-the-art manganese-zinc batteries are poorly rechargeable, owing to dendrite formation on the zinc anode. Organic materials could provide a safe and sustainable replacement. In the present work, a conducting redox polymer (CRP) based on a trimer of EPE (E=3,4-ethylenedioxythiophene; P=3,4-propylenedioxythiophene) and a naphthoquinone (NQ) pendant group is used as anode in polymer-manganese secondary batteries. The polymer shows stable redox conversion around+0.05 V vs. Ag/AgCl, and fast kinetics that involves proton cycling during pendant group redox conversion. For the first time, a CRP-manganese secondary battery was fabricated with pEP(NQ)E as the anode, manganese oxide as the cathode, and manganese-containing acidic aqueous solution as the electrolyte. This battery yielded a discharge voltage of 1.0 V and a discharging capacity of 76 mAh/ganode over >50 cycles and high rate capabilities (up to 10C).

    Download full text (pdf)
    fulltext
  • 30.
    Oka, Kouki
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. Department of Applied Chemistry, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 165-8555, Japan.
    Strietzel, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Nishide, Hiroyuki
    Department of Applied Chemistry, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 165-8555, Japan; Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 165-8555, Japan.
    Oyaizu, Kenichi
    Department of Applied Chemistry, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 165-8555, Japan; Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 165-8555, Japan.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Characterization of PEDOT-Quinone conducting redox polymers in water-in-salt electrolytes for safe and high-energy Li-ion batteries2019In: Electrochemistry communications, ISSN 1388-2481, E-ISSN 1873-1902, Vol. 105, article id 106489Article in journal (Refereed)
    Abstract [en]

    Li-ion batteries (LIBs) raise safety and environmental concerns, which mostly arise from their toxic and flammable electrolytes and the extraction of limited material resources by mining. Recently, water-in-salt electrolytes (WiSEs), in which a large amount of lithium salt is dissolved in water, have been proposed to allow for assembling safe and high-voltage (>3.0 V) aqueous LIBs. In addition, organic materials derived from abundant building blocks and their tunable properties could provide safe and sustainable replacements for inorganic cathode materials. In the current work, the electrochemical properties of a conducting redox polymer based on poly(3,4-ethylenedioxythiophene) (PEDOT) with hydroquinone (HQ) pendant groups have been characterized in WiSEs. The quinone redox reaction occurs within the potential region where the polymer is conducting, and fast redox conversion that involves lithium cycling during pendant group redox conversion was observed. These properties make conducting redox polymers promising candidates as cathode-active materials for safe and high-energy aqueous LIBs. An organic-based aqueous LIB, with a HQ-PEDOT as a cathode, Li4Ti5O12 (LTO) as an anode, and ca. 15 m lithium bis(trifluoromethanesulfonyl)imide water/dimethyl carbonate (DMC) as electrolyte, yielded an output voltage of 1.35 V and high rate capabilities up to 500C.

    Download full text (pdf)
    fulltext
  • 31.
    Oka, Kouki
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials. Department of Applied Chemistry, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 165-8555 Japan..
    Strietzel, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Nishide, Hiroyuki
    Department of Applied Chemistry, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 165-8555 Japan.; Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 165-8555 Japan..
    Oyaizu, Kenichi
    Department of Applied Chemistry, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 165-8555 Japan.; Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 165-8555 Japan..
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Conducting Redox Polymer as a Robust Organic Electrode-Active Material in Acidic Aqueous Electrolyte towards Polymer–Air Secondary Batteries2020In: ChemSusChem, ISSN 1864-5631, E-ISSN 1864-564X, Vol. 13, no 9, p. 2280-2285Article in journal (Refereed)
    Abstract [en]

    Organic materials receive increasing attention as environmentally benign and sustainable electrode-active materials. We present a conducting redox polymer (CRP) based on poly(3,4-ethylenedioxythiophene) with naphthoquinone pendant group, which is formed from a stable suspension of a trimeric precursor and an oxoammonium cation as oxidant. This suspension allows us to easily coat the polymer onto a current collector, opening up use of roll-to-roll processing or ink-jet printing for electrode preparation. The CRP showed a full capacity of 76?mAh?g?1 even at a high C rate of 100?C in acidic aqueous electrolyte. These properties make the CRP a promising candidate as anode-active material; a polymer?air secondary battery was fabricated with the CRP as anode, a conventional Pt/C catalyst as cathode, and sulfuric acid aqueous solution as electrolyte. This battery yielded a discharge voltage of 0.50?V and showed good cycling stability with 97?% capacity retention after 100 cycles and high rate capabilities up to 20C.

  • 32.
    Oka, Kouki
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials. Department of Applied Chemistry, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 165-8555 Japan..
    Strietzel, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Nishide, Hiroyuki
    Department of Applied Chemistry, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 165-8555 Japan.; Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 165-8555 Japan..
    Oyaizu, Kenichi
    Department of Applied Chemistry, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 165-8555 Japan.; Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 165-8555 Japan..
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Cover Feature: Conducting Redox Polymer as a Robust Organic Electrode-Active Material in Acidic Aqueous Electrolyte towards Polymer-Air Secondary Batteries (ChemSusChem 9/2020)2020In: ChemSusChem, ISSN 1864-5631, Vol. 13, no 9, p. 2105-2105Article in journal (Refereed)
    Abstract [en]

    The Cover Feature shows a polymer-air secondary battery composed of a naphthoquinone-based conducting redox polymer as a paintable and robust organic anode material and a Pt/C catalyst as a cathode-active material operating in an acidic aqueous electrolyte.

  • 33.
    Oka, Kouki
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials. Waseda Univ, Dept Appl Chem, Shinjuku Ku, 3-4-1 Okubo, Tokyo 1658555, Japan..
    Strietzel, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Nishide, Hiroyuki
    Waseda Univ, Dept Appl Chem, Shinjuku Ku, 3-4-1 Okubo, Tokyo 1658555, Japan.;Waseda Univ, Res Inst Sci & Engn, Shinjuku Ku, 3-4-1 Okubo, Tokyo 1658555, Japan..
    Oyaizu, Kenichi
    Waseda Univ, Dept Appl Chem, Shinjuku Ku, 3-4-1 Okubo, Tokyo 1658555, Japan.;Waseda Univ, Res Inst Sci & Engn, Shinjuku Ku, 3-4-1 Okubo, Tokyo 1658555, Japan..
    Strømme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Conducting Redox Polymer as a Robust Organic Electrode-Active Material in Acidic Aqueous Electrolyte towards Polymer-Air Secondary Batteries2020In: ChemSusChem, ISSN 1864-5631, E-ISSN 1864-564X, Vol. 13, no 9, p. 2280-2285Article in journal (Refereed)
    Abstract [en]

    Organic materials receive increasing attention as environmentally benign and sustainable electrode-active materials. We present a conducting redox polymer (CRP) based on poly(3,4-ethylenedioxythiophene) with naphthoquinone pendant group, which is formed from a stable suspension of a trimeric precursor and an oxoammonium cation as oxidant. This suspension allows us to easily coat the polymer onto a current collector, opening up use of roll-to-roll processing or ink-jet printing for electrode preparation. The CRP showed a full capacity of 76 mAh g(-1) even at a high C rate of 100 C in acidic aqueous electrolyte. These properties make the CRP a promising candidate as anode-active material; a polymer-air secondary battery was fabricated with the CRP as anode, a conventional Pt/C catalyst as cathode, and sulfuric acid aqueous solution as electrolyte. This battery yielded a discharge voltage of 0.50 V and showed good cycling stability with 97 % capacity retention after 100 cycles and high rate capabilities up to 20 C.

  • 34.
    Rouf, Alvi M.
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Tibbelin, Julius
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Jahn, Burkhard O.
    Anas, Saithalavi
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Lozinski, Kaitlin
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Efficient and convenient acid catalyzed hypersilyl protection of alcohols and thiols by tris(trimethylsilyl)silyl-N,N-dimethylmethaneamide2013In: Abstracts of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 245, p. 312-ORGN-Article in journal (Other academic)
  • 35.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sterby, Mia
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Hao
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Xiao
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    Gogoll, A
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Quinone-Substituted Conducting Polymers as Electrode Materials for All-Organic Proton Batteries2018Conference paper (Refereed)
  • 36.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sterby, Mia
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Hao
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Wang, Huan
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Conducting Redox Polymer Batteries2018Conference paper (Refereed)
  • 37.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sterby, Mia
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strietzel, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Yang, Li
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Hao
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Wang, Huan
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Xiao
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    Gogoll, A
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Conducting Redox Polymer Based Batteries2017Conference paper (Refereed)
  • 38.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sterby, Mia
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Åkerlund, Lisa
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Hao
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Xiao
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    Gogoll, Adolf
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Organic Batteries Based on Quinone-Substituted Conducting Polymers2017Conference paper (Refereed)
    Download full text (pdf)
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  • 39.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strietzel, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Wang, Huan
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sterby, Mia
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Designing Quinone-based Conducting Redox Polymers specifically for Aqueous Proton Batteries and for Lithium Ion Battery Cathodes2020Conference paper (Refereed)
    Abstract [en]

     Conducting redox polymers (CRPs) are conducting polymers that have been decorated with redox active functional groups and they provide an attractive alternative as organic matter based electrical energy storage materials. The purpose of the polymer backbone is two-fold, 1) it prevents dissolution of the redox group and, 2) it renders the material conductive. The redox active pendant groups, on the other hand, provide the material with a well-defined redox reaction as well as a high charge storage capacity. CRPs thus provide a solution to two of the most significant obstacles in achieving powerful and stable battery materials from organic compounds, i.e. materials dissolution and limited electronic conductivity while simultaneously providing a high charge storage capacity. For battery applications it is thus essential that the individual properties of the conducting polymer backbone and the redox group can be preserved and that they operate in synergy in the CRP. One prerequisite for synergetic polymer-pendant combinations is redox matching. As conducting polymers are only conducting in their charged state successful combinations rely on that the pendant group has a redox potential within the conducting region of the polymer backbone. In addition, the CRP must allow mass transport of ions, not only related to the cycling chemistry of the pendant group but also ions related to the doping of the polymer backbone. These requirements put significantly different demands on the polymer design for the development of aqueous proton batteries and for CRPs for lithium cycling cathodes. In this presentation specific CRP design-solutions will be presented that allow for the development of all-organic proton batteries 1,2 and for lithium ion CRP-battery cathodes 3. 

    In addition, a solution-processing method, termed Post Deposition Polymerization (PDP), for CRP-materials and the underlying principles and requirements for PDP will be presented. Importantly, in PDP the processing step occurs prior to polymerization. After depositing and drying of the repeat-unit precursor onto a substrate polymerization is achieved by oxidative polymerization of the precursor. The PDP-method opens up for a scalable method for the coating of CRP materials onto any substrate and can, for instance, be used to make nanostructured CRP materials.

    1              Emanuelsson, R., Sterby, M., Strømme, M. & Sjödin, M. An All-Organic Proton Battery. J. Am. Chem. Soc. 139, 4828-4834, doi:10.1021/jacs.7b00159 (2017).

    2              Strietzel, C. et al. Accepted in Angewandte Chemie doi:10.1002/anie.202001191 (2020).

    3              Wang, H. et al. Redox-State-Dependent Interplay between Pendant Group and Conducting Polymer Backbone in Quinone-Based Conducting Redox Polymers for Lithium Ion Batteries. ACS Applied Energy Materials 2, 7162-7170, doi:10.1021/acsaem.9b01130 (2019).

  • 40.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials. Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    Strietzel, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Wang, Huan
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Conducting Redox Polymers as Active Materials in Secondary Batteries2023In: 74th Annual Meeting of the International Society of Electrochemistry / [ed] International Society of Electrochemistry, 2023Conference paper (Refereed)
  • 41.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Wang, Huan
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Åkerlund, Lisa
    Sterby, Mia
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Hao
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Gogoll, A
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Organiska batterier för hållbar och ökad energi-effektivitet i lokal energilagring2018Conference paper (Other academic)
  • 42.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Hao
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sterby, Mia
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Xiao
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Yang, Li
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Karlsson, Christoffer
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Gogoll, Adolf
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Conducting Redox Polymers for Secondary Batteries2016Conference paper (Refereed)
  • 43.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Karlsson, Christoffer
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Hao
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Yang, Li
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Xiao
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanielsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Gogoll, Adolf
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry.
    Rational design of conducting redox polymers for electrical energy storage2015Conference paper (Refereed)
  • 44.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Karlsson, Christoffer
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Huang, Hao
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Yang, Li
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Xiao, Huang
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Gogoll, Adolf
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry.
    Design principles for constructing conducting redox polymer based battery materials2015Conference paper (Refereed)
  • 45.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Rikard, Emanuelsson
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strietzel, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Wang, Huan
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Conducting Redox Polymers as Active Materials in Secondary Batteries2023Conference paper (Refereed)
  • 46.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Sterby, Mia
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strietzel, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Wang, Huan
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Conducting Redox Polymers as Electrical Energy Storage Materials2019Conference paper (Refereed)
    Abstract [en]

    Conducting redox polymers (CRPs) is an attractive alternative as organic matter based electrical energy storage materials as they provide means of combining the favorable charge transport properties of conducting polymers with the high capacity and well defined redox chemistry of small redox active groups. In general CRPs are composed of a conducting polymer backbone where each or some of the monomers building up the polymer is bearing a redox active functional group. Although the working principle of CRPs is straightforward several key criteria need to be met in the CRP design in order to benefit from synergetic effects of the conducting polymer backbone and the pendent group in CRPs that will be outlined in this presentation: 1) As conducting polymers are only conducting in their charged state successful polymer-pendent group combinations rely on that the pendant group has a redox potential within the conducting region of the polymer backbone. This condition is referred to as redox matching and the requirement in the CRP design will be explicitly proven.[1] 2) The purpose of the polymer backbone is to provide efficient electron transport through the material. We have previously shown the polymer conductivity can be severely compromised by the pendant group.[2] This could be overcome by judicious choice of polymer backbone and results will be presented that show that non-activated (semi-metallic) electron transport can be achieved in CRPs.[3-4] 3) A final design principle that will be discussed is related to the polymerizability and how it is affected by the nature of the link between the polymer backbone and the pendent.[5] In addition a novel polymerization method for CRP monomers will be presented that allow bulk processing even for insoluble CRPmaterials.

  • 47.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Strietzel, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Conducting redox oligomers2022Patent (Other (popular science, discussion, etc.))
    Abstract [en]

    The present disclosure relates to compounds of formula IVa or IVb, or salts thereof, as intermediates in the manufacture of conducting redox polymers. L is a covalent linker moiety and R is a reversible redox group. The disclosure further relates to conducting redox polymers produced from such compounds, as well as substrates coated with such conducting redox polymers, and organic batteries comprising such conducting redox polymers.

  • 48.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Strietzel, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Conducting redox oligomers2022Patent (Other (popular science, discussion, etc.))
    Abstract [en]

    The present disclosure relates to compounds of formula IVa or IVb, or salts thereof, as intermediates in the manufacture of conducting redox polymers. L is a covalent linker moiety and R is a reversible redox group.The disclosure further relates to conducting redox polymers produced from such compounds, as well as substrates coated with such conducting redox polymers, and organic batteries comprising such conducting redox polymers.

  • 49.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.
    Strietzel, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Conducting redox oligomers2022Patent (Other (popular science, discussion, etc.))
  • 50.
    Sjödin, Martin
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Strietzel, Christian
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Wang, Huan
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Kouki, Oka
    Åkerlund, Lisa
    Strömme, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Quinone-Based Conducting Redox Polymers as Active Materials for Secondary Batteries2021Conference paper (Refereed)
123 1 - 50 of 101
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