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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, ISSN 2046-2069, 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 1420-3049, 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).

  • 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: 2016-03-08Bibliographically 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
    Show others...
    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
  • 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.
    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.

  • 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: 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.

  • 7.
    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.

  • 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.
    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.

  • 9.
    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.

  • 10.
    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: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 245, p. 1246-INOR-Article in journal (Other academic)
  • 11.
    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.

  • 12.
    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.

  • 13.
    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.

  • 14.
    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.

  • 15.
    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: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 247, article id 560-ORGNArticle in journal (Other academic)
  • 16.
    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.

  • 17.
    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)
  • 18.
    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.

  • 19.
    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 (Online), 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.

  • 20.
    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: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 245, p. 312-ORGN-Article in journal (Other academic)
  • 21.
    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, Adolf
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    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)
  • 22.
    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)
  • 23.
    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)
  • 24.
    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)
  • 25.
    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)
  • 26.
    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)
  • 27.
    Sterby, Mia
    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.
    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.
    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 for Water Based Secondary Batteries2017In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 235, p. 356-364Article in journal (Refereed)
    Abstract [en]

    Lithium-ion technologies show great promise to meet the demands that the transition towards renewable energy sources and the electrification of the transport sector put forward. However, concerns regarding lithium-ion batteries, including limited material resources, high energy consumption during production, and flammable electrolytes, necessitate research on alternative technologies for electrochemical energy storage. Organic materials derived from abundant building blocks and with tunable properties, together with water based electrolytes, could provide safe, inexpensive and sustainable alternatives. In this study, two conducting redox polymers based on poly(3,4-ethylenedioxythiophene) (PEDOT) and a hydroquinone pendant group have been synthesized and characterized in an acidic aqueous electrolyte. The polymers were characterized with regards to kinetics, pH dependence, and mass changes during oxidation and reduction, as well as their conductance. Both polymers show redox matching, i.e. the quinone redox reaction occurs within the potential region where the polymer is conducting, and fast redox conversion that involves proton cycling during pendant group redox conversion. These properties make the presented materials promising candidates as electrode materials for water based all-organic batteries.

  • 28.
    Sterby, Mia
    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.
    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.
    Electronic properties of a PEDOT/Quinone Conducting Redox Polymer2018Conference paper (Other academic)
    Abstract [en]

    Organic materials can be used to ensure sustainable electrical energy storage, thus avoiding the use of inorganic materials that are inherently non-renewable and associated with large energy consumptions in their mining and refining. To ensure sufficient conductivity, most organic batteries researched on today use conducting additives since organic molecules, in general, are insulating. A different approach is to use conducting redox polymers (CRPs). CRPs consist of a redox active pendant group attached to a conducting polymer backbone.

     

    The present work focuses on characterizing a cathode material for water based batteries. The material consists of the well-studied conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) with a quinone pendant group, a combination that we have proven can work in an all-organic proton battery.1 Quinones constitute an attractive class of molecules as they possess a high charge storage capacity, show reversible redox chemistry, and are naturally occurring, e.g., in the electron transport chains in photosynthesis and in respiration.

     

    Redox matching (i.e. the redox reaction of the pendant group occurring at a potential where the polymer is conducting) between the conducting polymer and the pendant group is crucial for CRPs since the electrons stored in the pendant groups have to travel through the polymer to the current collector. From in situ conductance measurements we have previously shown that redox matching exists in the studied CRP.2 In this work we present studies of the redox matched CRP showing a non-activated electron transport through the polymer backbone, an activated process for the quinone redox conversion, and indication of polarons being the dominant charge carrier. The reorganization energy of the quinone as well as ion mobility through the polymer will also be discussed.

     

     

     

     

     

    1. Emanuelsson, R.; Sterby, M.; Strømme, M.; Sjödin, M., An All-Organic Proton Battery. J. Am. Chem. Soc. 2017, 139 (13), 4828-4834.

    2. Sterby, M.; Emanuelsson, R.; Huang, X.; Gogoll, A.; Strømme, M.; Sjödin, M., Characterization of PEDOT-Quinone Conducting Redox Polymers for Water Based Secondary Batteries. Electrochim. Acta 2017, 235, 356–364.

  • 29.
    Sterby, Mia
    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.
    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.
    In Situ Methods for Understanding Charge Transport in a Conducting Redox Polymer2018In: Materials Research Society. Fall meeting 2018. Boston: Excitons, Electrons and Ions in Organic Materials / [ed] MRS, Boston, 2018, article id EP05.01.07Conference paper (Refereed)
    Abstract [en]

    Organic materials can be used to ensure sustainable electrical energy storage, but since organic molecules are generally insulating conducting additives are commonly used to ensure electrical conductivity throughout the material. A different approach is to use conducting redox polymers (CRPs). CRPs consist of a redox active pendant group, used for its high capacity, attached to a conducting polymer backbone. The CRP presented here is aimed to be used as the positive electrode in a water-based organic battery. In this work we employ the well-studied conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) with a quinone pendant group, a combination that we have proven can work in an all-organic proton battery.

    1 Quinones constitute an attractive class of molecules as they possess a high charge storage capacity, show reversible redox chemistry, and are naturally occurring, e.g., in the electron transport chains in respiration and in photosynthesis. The aim of the study is to understand the charge transport properties of the CRP. The CRP studied is characterized by various in-situ electrochemical methods including conductance, Quartz Crystal Microbalance (QCM), UV-vis and Electron Paramagnetic Resonance (EPR). Based on the results the electron and ion transport during electrochemical redox conversion will be discussed. 1. Emanuelsson, R.; Sterby, M.; Strømme, M.; Sjödin, M., An All-Organic Proton Battery. J. Am. Chem. Soc. 2017, 139 (13), 4828-4834.

  • 30.
    Sterby, Mia
    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.
    Strømme, Maria
    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.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Characterization of a PEDOT/Quinone Conducting Redox Polymer2016Conference paper (Other academic)
    Abstract [en]

    Organic materials can be used to ensure sustainable electrical energy storage, thus avoiding the use of inorganic materials that are inherently non-renewable and associated with large energy consumptions in their mining and refining. One category of organic energy storage materials consists of conducting redox polymers (CRPs). They include a conducting polymer backbone (CP), a redox active pendant group (PG), and a linker attaching the PG to the CP. The present work involves the CP poly(3,4-ethylenedioxythiophene) (PEDOT) and a quinone PG in acidic water solution. Quinones constitute an attractive class of molecules as they show reversible redox chemistry in several electrolyte systems, possess a high charge storage capacity and are naturally occurring e.g. in the electron transport chains in respiration and in photosynthesis. The CRP studied is characterized by cyclic voltammetry as well as by EQCM, in-situ conductance, and in-situ spectroscopic methods. In this work we present the formal potential of the quinone, the rate constant for electron transport in the polymer, mass changes during electrochemical redox conversion in different potential regions, and conductance data providing support for a CP-mediated electron transport through the material. Based on the results the electron and ion transport during electrochemical redox conversion will be discussed.                                                                                              

  • 31.
    Sterby, Mia
    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.
    Strømme, Maria
    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.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Linker Effect in PEDOT/Quinone Organic Battery Materials2016Conference paper (Refereed)
    Abstract [en]

    One way to ensure sustainable electrical energy storage is to use organic materials. Organic materials can be made from renewable resources and thus the use of limited resources needed for inorganic materials is avoided. Conducting redox polymers (CRPs) are one type of organic material that can be used in e.g. batteries. CRPs consist of a conducting polymer backbone, a redox active pendant group, and a linker connecting the pendant group to the polymer. The present work focuses on the well-studied conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) with quinone pendant groups in water based systems. Quinones constitute a class of redox active molecules used in nature e.g. for electron transport in photosynthesis and in respiration. Although the third unit, the linker, is a passive part in the system it can greatly impact the behavior of the resulting CRP. In this report we present scan rate dependent voltammetric data as well as EQCM and in-situ conductance on two CRPs differing only by two CH2 groups in the linker. Figure 1 shows molecular structure, CV, and EQCM data of I and II indicating the significant influence that the minor difference in the linking unit has on the redox chemistry in these systems.

  • 32. Strietzel, Christian
    et al.
    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 Engineering Sciences, Solid State Physics.
    Sjödin, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Conducting Redox Polymer Batteries2018Conference paper (Refereed)
  • 33.
    Strietzel, Christian
    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.
    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.
    Flexible All Organic Batteries Based on Conducting Redox Polymers2018In: MRS Fall meeting 2018: Flexible/Wearable Energy Storage I / [ed] MRS, Boston, 2018, article id BM08.11.02Conference paper (Refereed)
    Abstract [en]

    Batteries consisting of naturally occurring organic materials can be envisioned as sustainable alternatives to conventional metal-based batteries, thus

    avoiding the negative environmental impact associated with the production and recycling of the latter. In this way the negative environmental impact of the

    constantly increasing demand for secondary batteries can be decreased. Apart from being fully organic, such batteries also open up for flexible battery

    designs as they can be produced in a roll-to-roll process and they are anticipated to be viable in a broad range of applications as energy supplies in

    innovative flexible electronics designs. In the current work, fully organic batteries are realized utilizing conducting redox polymers (CRPs) as electrode

    materials. CRPs combine the high charge storage capacity of a redox active pendant group (PG) with the conduction properties of a conducting polymer

    (CP) backbone, both to reduce the need for addition of conductive carbon black and increasing the stability of the PG redox conversion in a battery setup.

    The first results from a fully organic, aqueous battery based on CRP electrode material are presented. Challenges and possibilities of this type of battery in flexible battery designs are discussed.

  • 34.
    Tibbelin, Julius
    et al.
    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.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Heijkenskjöld, Filip
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Rosenberg, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Yamazaki, Kaoru
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Nauroozi, Djawed
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
    Karlsson, Leif
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Feifel, Raimund
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Pettersson, Roland
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Analytical Chemistry.
    Baumgartner, Judith
    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, Synthetical Organic Chemistry.
    1,4-Disilacyclohexa-2,5-diene: a molecular building block that allows for remarkably strong neutral cyclic cross-hyperconjugation2014In: Chemical Science, ISSN 2041-6520, Vol. 5, no 1, p. 360-371Article in journal (Refereed)
    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.

  • 35.
    Wallner, Andreas
    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.
    Baumgartner, Judith
    Marschner, Christoph
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
    Coupling of Disilane and Trisilane Segments Through Zero, One, Two, and Three Disilanyl Bridges in Cyclic and Bicyclic Saturated Carbosilanes2013In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 32, no 2, p. 396-405Article in journal (Refereed)
    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.

  • 36.
    Wang, Huan
    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.
    Sjödin, Martin
    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.
    Electrochemical Performance of Electron Withdrawing Group Substituted Benzoquinone and Benzoquinone-Functionalized Poly(3,4-ethylenedioxythiophene) Conducting Redox Polymer2018In: MRS Fall meeting 2018: In Situ/Operando Analysis of Electrochemical Materials and Interfaces / [ed] MRS, Boston, 2018, article id CM03.09.03Conference paper (Refereed)
    Abstract [en]

    Conducting redox polymers have been investigate massively as an efficient cathode material. Herein we synthesis a series of quinone substituted PEDOT conducting redox polymers and investigate the effect of electron withdrawing substitutions on the redox potential of quinone in the PEDOT backbone in two electrolyte 0.1M LiClO4/MeCN a. Elelctron withdrawing substitutions leads to an increase of the redox potential of quinone in LiClO4/MeCN . The conductivity of PEDOT backbone is hindered by the lithiated reduced quinone. In-situ uv-vis and EQCM is used to probe the exact PEDOT doping onset potential, confirming that conductivity of quinone is hindered by lithiated reduced quinone. In situ EQCM proves that mass change in the PEDOT doping region involves cation repulsion and dopants anion uptaken.

  • 37.
    Wang, Huan
    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.
    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 redox potential tunning and characterization of quinone-PEDOT as a lithium cathode2018Conference paper (Other academic)
  • 38.
    Wångsell, Fredrik
    et al.
    Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Pharmacy, Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry.
    Nordeman, Patrik
    Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Pharmacy, Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry.
    Sävmarker, Jonas
    Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Pharmacy, Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry.
    Emanuelsson, Rikard
    Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Pharmacy, Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry.
    Jansson, Katarina
    Lindberg, Jimmy
    Rosenquist, Åsa
    Samuelsson, Bertil
    Larhed, Mats
    Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Pharmacy, Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry. Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Pharmacy, Department of Medicinal Chemistry, Preclinical PET Platform.
    Investigation of alpha-phenylnorstatine and alpha-benzylnorstatine as transition state isostere motifs in the search for new BACE-1 inhibitors2011In: Bioorganic & Medicinal Chemistry, ISSN 0968-0896, E-ISSN 1464-3391, Vol. 19, no 1, p. 145-155Article in journal (Refereed)
    Abstract [en]

    Inhibition of the BACE-1 protease enzyme has over the recent decade developed into a promising drug strategy for Alzheimer therapy. In this report, more than 20 new BACE-1 protease inhibitors based on α-phenylnorstatine, α-benzylnorstatine, iso-serine, and β-alanine moieties have been prepared. The inhibitors were synthesized by applying Fmoc solid phase methodology and evaluated for their inhibitory properties. The most potent inhibitor, tert-alcohol containing (R)-12 (IC50 = 0.19 μM) was co-crystallized in the active site of the BACE-1 protease, furnishing a novel binding mode in which the N-terminal amine makes a hydrogen bond to one of the catalytic aspartic acids.

  • 39.
    Åkerlund, Lisa
    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.
    Gogoll, Adolf
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    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 Renewable Energy Storage2016Conference paper (Refereed)
    Abstract [en]

    To meet future energy needs and to minimize CO2-emissions, a higher share of produced electricity must come from renewable resources [1]. Unfortunately, the output of renewable energy sources varies and does not always correlate with the temporal demand for electricity. For this reason, high capacity electrical energy storage (EES) is needed to fully utilize renewable energy sources [2]. Today’s battery technologies primarily rely on metals extracted at large economic and environmental costs [3],and the benefits of converting to carbon based materials are several, e.g. lower weight, flexible materials, and better recycling possibilities. In addition, the total energy consumption in the production chain may be reduced if the high temperatures required for extracting and processing metals can be avoided. Conducting redox polymers (CRPs), i.e. conducting polymers with redox active side groups, are currently investigated as possible organic electrode materials [4]. In this work we focus on finding stable side groups with high charge storage capacity. Quinones, which occur in natural energy conversion systems, i.e. during photosynthesis and respiration, are an attractive side group for CRPs due to their high gravimetric capacity. Importantly, for a functioning battery application the redox group and the polymer backbone must be active in the same potential window and this can be tuned effectively over a wide potential range by substitution on the quinone ring; hence various quinone derivatives could match different polymer backbones. A high potential- and high charge capacity quinone derivative has been synthesized and electrochemically characterized with the aim of producing a novel CRP to function as an organic high charge capacity material, targeting renewable organic batteries for a future of sustainable EES.

     

    References

    [1]  D. Larcher, J. M. Tarascon,, Nat. Chem. 7 (2015) 19-29.

    [2] Z. Yang, J. Zhang, M. C. W. Kintner-Meyer, X. Lu, D. Choi, J. P. Lemmon, J. Liu, Chem. Rev. 111 (2011) 3577–3613.

    [3] P. Poizot, F. Dolhem, Energy Environ. Sci. 4 (2011) 2003-2019.

    [4] (a) C. Karlsson, H. Huang, M. Stromme, A. Gogoll, M. Sjodin, RSC Adv. 5 (2015) 11309-11316; (b) C. Karlsson, H. Huang, M. Stromme, A. Gogoll, M. Sjodin, Electrochim. Acta 179 (2015) 336-342.

    [5] L. Åkerlund, R. Emanuelsson, A. Gogoll, M. Strömme, M. Sjödin, To be submitted.

  • 40.
    Åkerlund, Lisa
    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.
    Gogoll, Adolf
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    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.
    Quinone based Conducting Redox Polymers for Renewable Energy Storage2016Conference paper (Refereed)
    Abstract [en]

    To meet future energy needs and to minimize CO2-emissions, a higher share of produced electricity must come from renewable resources [1]. Unfortunately, the output of renewable energy sources varies and does not always correlate with the temporal demand for electricity. For this reason, high capacity electrical energy storage (EES) is needed to fully utilize renewable energy sources [2]. Today’s battery technologies primarily rely on metals extracted at large economic and environmental costs [3],and the benefits of converting to carbon based materials are several, e.g. lower weight, flexible materials, and better recycling possibilities. In addition, the total energy consumption in the production chain may be reduced if the high temperatures required for extracting and processing metals can be avoided. Conducting redox polymers (CRPs), i.e. conducting polymers with redox active side groups, are currently investigated as possible organic electrode materials [4]. In this work we focus on finding stable side groups with high charge storage capacity. Quinones, which occur in natural energy conversion systems, i.e. during photosynthesis and respiration, are an attractive side group for CRPs due to their high gravimetric capacity. Importantly, for a functioning battery application the redox group and the polymer backbone must be active in the same potential window and this can be tuned effectively over a wide potential range by substitution on the quinone ring; hence various quinone derivatives could match different polymer backbones. A high potential- and high charge capacity quinone derivative has been synthesized and electrochemically characterized with the aim of producing a novel CRP to function as an organic high charge capacity material, targeting renewable organic batteries for a future of sustainable EES.

     

    References

    [1]  D. Larcher, J. M. Tarascon,, Nat. Chem. 7 (2015) 19-29.

    [2] Z. Yang, J. Zhang, M. C. W. Kintner-Meyer, X. Lu, D. Choi, J. P. Lemmon, J. Liu, Chem. Rev. 111 (2011) 3577–3613.

    [3] P. Poizot, F. Dolhem, Energy Environ. Sci. 4 (2011) 2003-2019.

    [4] (a) C. Karlsson, H. Huang, M. Stromme, A. Gogoll, M. Sjodin, RSC Adv. 5 (2015) 11309-11316; (b) C. Karlsson, H. Huang, M. Stromme, A. Gogoll, M. Sjodin, Electrochim. Acta 179 (2015) 336-342.

    [5] L. Åkerlund, R. Emanuelsson, A. Gogoll, M. Strömme, M. Sjödin, To be submitted.

  • 41.
    Åkerlund, Lisa
    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.
    Renault, Stevén
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Huang, Hao
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Brandell, Daniel
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural 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.
    The Proton Trap Technology: Toward High Potential Quinone-Based Organic Energy Storage2017In: Advanced Energy Materials, ISSN 1614-6840, Vol. 7, no 20, article id 1700259Article in journal (Refereed)
    Abstract [en]

    An organic cathode material based on a copolymer of poly(3,4-ethylenedioxythiophene) containing pyridine and hydroquinone functionalities is described as a proton trap technology. Utilizing the quinone to hydroquinone redox conversion, this technology leads to electrode materials compatible with lithium and sodium cycling chemistries. These materials have high inherent potentials that in combination with lithium give a reversible output voltage of above 3.5 V (vs Li0/+) without relying on lithiation of the material, something that is not showed for quinones previously. Key to success stems from coupling an intrapolymeric proton transfer, realized by an incorporated pyridine proton donor/acceptor functionality, with the hydroquinone redox reactions. Trapping of protons in the cathode material effectively decouples the quinone redox chemistry from the cycling chemistry of the anode, which makes the material insensitive to the nature of the electrolyte cation and hence compatible with several anode materials. Furthermore, the conducting polymer backbone allows assembly without any additives for electronic conductivity. The concept is demonstrated by electrochemical characterization in several electrolytes and finally by employing the proton trap material as the cathode in lithium and sodium batteries. These findings represent a new concept for enabling high potential organic materials for the next generation of energy storage systems.

  • 42.
    Åkerlund, Lisa
    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.
    Sjödin, Martin
    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.
    Organic Polymeric Materials for Renewable Batteries2015Conference paper (Refereed)
    Abstract [en]

    To solve for future energy needs, capacity of storing energy will be crucial. In principle all of today’s batteries are made of metals, which are energy demanding to extract and recycle, as well as being non-renewable. A proposed alternative is to make batteries with same or higher charge capacity from renewable sources. Electrodes can be based on conducting redox polymers (CRPs) consisting of a polymeric backbone, such as PEDOT, with redox active side groups attached. As side groups, quinone derivatives can be utilized. Quinones function as charge carrier in nature’s photosynthesis. For a functioning battery application, redox group and polymer must be active in the same potential window and this can be tuned by changing functionality of the side groups. This project aims at finding and synthesizing high charge capacity CRP materials and targeting renewable organic batteries for a future of sustainable energy storage.

  • 43.
    Åkerlund, Lisa
    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.
    Strömme, M
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Martin, Sjödin
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
    Conducting Redox Polymers for Renewable Energy Storage2016Conference paper (Refereed)
  • 44.
    Åkerlund, Lisa
    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.
    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.
    The proton trap – a new route to high potential organic energy storage2018Conference paper (Refereed)
    Abstract [en]

    Floods, droughts and unpredictable weather could be the new normal state and reality for millions of people in a near future, unless we drastically decrease our greenhouse gas emissions so that the temperature increase can be kept below 2°C, as was agreed upon at the climate meeting in Paris 2015. To tackle environmental issues, material innovations will most certainly be essential for many of the technical solutions needed. One of the major challenges we are facing is how to deal with the massive energy demand following the average lifestyle of today in a way that is both reliable and sustainable. Renewable energy sources have a varying output over time and cannot by themselves meet these requirements; hence ways to store the energy is crucial. Our work is aimed at finding and developing new organic materials for energy storage that can contribute to a better alternative than the batteries that are on the market today. Many aspects of the resource exploitation for making a lithium ion battery are far from sustainable and, with the increasing number of electronic devices for numerous applications, we need new options. One way to make organic energy storage is to combine a conducting polymer backbone with a redox active pendant group, as to combine the features of conductivity and insolubility brought by the polymer backbone with the capacity of the pendant group. For this combination to be applicable the two parts must match in their respective activity windows. Additionally, one also needs to have a matching electrolyte system, in which the energy storage material is cycling reversibly at a reasonable scan rate and where no degradation occurs, to get a fully viable system for practical applications.

    In this work[1] we have developed new copolymers for organic energy storage containing something we call the proton trap. The proton trap system enables reversible cycling of hydroquinones, which, in comparison to their lithiated analogues, can provide a higher energy density originating in the higher redox potential. The proton trap system is based on incorporating a proton acceptor into the compound, which enables reversible proton transfer during redox-cycling. Thanks to the proton trap system, the redox processes of hydroquinone compounds can be utilized in many different electrolytes, without the use of coordinating salts (e.g. Li-salts) or protic solvents (as in aqueous electrolytes).

    With a cathode based on the pure proton trap material (no additives) and Li-foil as the anode, functioning batteries were assembled and characterized. After the publication of this study, the problems connected to the linker unit have been targeted and new results continue to take us small steps forward in the work targeting renewable organic batteries for a future of sustainable energy storage. When also finding a functioning and sustainable anode material we can enable fully organic based battery systems, enabling a closed loop of renewable energy production and storage, which is something we need in order to keep the climate changes under control.

    [1] Åkerlund, L., Emanuelsson, R., Renault, S., Huang, H., Brandell, D., Strømme, M., Sjödin M. (2017). The proton trap Technology—Toward high potential quinone‐based organic energy storage. Advanced Energy Materials, 7(20), 1700259.

  • 45.
    Åkerlund, Lisa
    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.
    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.
    Organic Polymeric Materials for Renewable Energy Storage2016Conference paper (Refereed)
    Abstract [en]

    To solve for future energy needs, the capacity of storing energy will be crucial when energy production from renewables increases. In principle all of today’s batteries are made of metals, which are energy demanding both to extract and recycle, as well as being non-renewable. An example is lithium ion batteries (LIBs), which today are unprofitable to recycle (due to the high temperatures needed), hence remaining deposits will not last for long if we want electric vehicles based on LIBs to replace conventional vehicles. Additionally, an electric car must be charged over 120 times before it even reaches a negative CO2 impact, compared to conventional cars. A solution to this problem is to make batteries with the same or higher charge capacity as conventional batteries, but from renewable sources.

    Quinones have high specific capacity and function as charge carriers in natures’ photosynthesis and respiration cycle. When combined with a polymeric backbone, the resulting material has potential of becoming a cheaper, lighter and greener alternative to LIBs.

    Conducting redox polymers (CRPs) have been proposed as a renewable alternative for electrode materials. CRPs consist of two parts: a conducting polymeric (CP) backbone, such as polypyrrole (PPy) or Poly(3,4-ethylenedioxythiophene) (PEDOT); and a redox active side group, such as quinones, attached to the backbone. For the system to function as a battery, the attached redox group must be active in the same potential window as the specific polymer is conducting.

    This project aims at finding, synthesizing and characterizing high charge capacity materials and targeting renewable organic batteries for a future of sustainable energy storage.

1 - 45 of 45
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