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Publications (10 of 66) Show all publications
Wani, I. H., Jafri, S. H., Wärnå, J., Hayat, A., Li, H., Shukla, V. A., . . . Leifer, K. (2019). A sub 20 nm metal-conjugated molecule junction acting as a nitrogen dioxide sensor. Nanoscale, 11(14), 6571-6575
Open this publication in new window or tab >>A sub 20 nm metal-conjugated molecule junction acting as a nitrogen dioxide sensor
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2019 (English)In: Nanoscale, ISSN 2040-3364, E-ISSN 2040-3372, Vol. 11, no 14, p. 6571-6575Article in journal (Refereed) Published
Abstract [en]

The interaction of a gas molecule with a sensing material causes the highest change in the electronic structure of the latter, when this material consists of only a few atoms. If the sensing material consists of a short, conductive molecule, the sensing action can be furthermore probed by connecting such molecules to nanoelectrodes. Here, we report that NO2 molecules that adhere to 4,4'-biphenyldithiol (BPDT) bound to Au surfaces lead to a change of the electrical transmission of the BPDT. The related device shows reproducible, stable measurements and is so far the smallest (<20 nm) gas sensor. It demonstrates modulation of charge transport through molecules upon exposure to nitrogen dioxide down to concentrations of 55 ppb. We have evaluated several devices and exposure conditions and obtained a close to linear dependence of the sensor response on the gas concentration.

National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-381056 (URN)10.1039/c8nr08417c (DOI)000464454400007 ()30916070 (PubMedID)
Funder
Swedish Research CouncilKnut and Alice Wallenberg FoundationGöran Gustafsson Foundation for Research in Natural Sciences and MedicineCarl Tryggers foundation Swedish Energy AgencySwedish Foundation for Strategic Research
Available from: 2019-04-03 Created: 2019-04-03 Last updated: 2019-05-03Bibliographically approved
Orthaber, A. (2019). Andreas Orthaber. European Journal of Inorganic Chemistry (11-12), 1441-1442
Open this publication in new window or tab >>Andreas Orthaber
2019 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, no 11-12, p. 1441-1442Article in journal, Editorial material (Other academic) Published
Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2019
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-382022 (URN)10.1002/ejic.201900194 (DOI)000462351000003 ()
Available from: 2019-04-23 Created: 2019-04-23 Last updated: 2019-04-23Bibliographically approved
Devaraj, K., Ingner, F., Sollert, C., Gates, P. J., Orthaber, A. & Pilarski, L. T. (2019). Arynes and Their Precursors from Arylboronic Acids via Catalytic C-H Silylation. Journal of Organic Chemistry, 84(9), 5863-5871
Open this publication in new window or tab >>Arynes and Their Precursors from Arylboronic Acids via Catalytic C-H Silylation
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2019 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 84, no 9, p. 5863-5871Article in journal (Refereed) Published
Abstract [en]

A new, operationally simple approach is presented to access arynes and their fluoride-activated precursors based on Ru-catalyzed C-H silylation of arylboronates. Chromatographic purification may be deferred until after aryne capture, rendering the arylboronates de facto precursors. Access to various new arynes and their derivatives is demonstrated, including, for the first time, those based on a 2,3-carbazolyne and 2,3-fluorenyne core, which pave the way for novel derivatizations of motifs relevant to materials chemistry.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2019
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-387960 (URN)10.1021/acs.joc.9b00221 (DOI)000467319600089 ()30835118 (PubMedID)
Funder
Swedish Research CouncilCarl Tryggers foundation
Available from: 2019-06-27 Created: 2019-06-27 Last updated: 2019-06-27Bibliographically approved
Green, J. P., Gupta, A. K. & Orthaber, A. (2019). Effect of Arsenic Coordination State on the Structure, Aromaticity, and Optical Properties of Dithieno[3,2-b:2 ',3 '-d]arsoles. European Journal of Inorganic Chemistry (11-12), 1539-1543
Open this publication in new window or tab >>Effect of Arsenic Coordination State on the Structure, Aromaticity, and Optical Properties of Dithieno[3,2-b:2 ',3 '-d]arsoles
2019 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, no 11-12, p. 1539-1543Article in journal (Refereed) Published
Abstract [en]

A silylated derivative of 4-phenyl-dithieno[3,2-b:2 ',3 '-d]arsole (DTAs) was synthesized, and the effect of coordinating of DTAs compounds to Pd on their structural and optical properties was investigated. Coordination of the As to Pd was found to increase the structural aromaticity of the ring system as measured by the harmonic oscillator measure of heterocyclic electron delocalization (HOMHED), and the pyramidalization of the As atoms was also found to show a good correlation with the HOMHED values. However, coordination had a more subtle impact on the optical properties than seen for phosphorus-containing analogues as the metal-ligand interactions were weaker.

Keywords
Dithienoarsole, Aromaticity, Luminescence, Palladium complex, Arsenic
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-381571 (URN)10.1002/ejic.201801169 (DOI)000462351000012 ()
Funder
Swedish Research CouncilSwedish Energy AgencyCarl Tryggers foundation
Note

Correction in: Eur. J. Inorg. Chem. 2019, 1706

DOI: 10.1002/ejic.201900057

Available from: 2019-04-12 Created: 2019-04-12 Last updated: 2019-04-23Bibliographically approved
Pammer, F., Schepper, J., Gloeckler, J., Sun, Y. & Orthaber, A. (2019). Expansion of the scope of alkylboryl-bridged N -> B-ladder boranes: new substituents and alternative substrates. Dalton Transactions, 48(27), 10298-10312
Open this publication in new window or tab >>Expansion of the scope of alkylboryl-bridged N -> B-ladder boranes: new substituents and alternative substrates
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2019 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 48, no 27, p. 10298-10312Article in journal (Refereed) Published
Abstract [en]

A series of new boranes capable of forming intramolecular N -> B-heterocycles has been prepared and their properties have been studied by electrochemical methods and UV-vis-spectroscopy complemented by DFT calculations. A dimethylborane (BMe2), haloborane derivatives (BBr2, BF2, BI2) and mixed cyano/isocyano-borane (B(CN)(NC)) have been prepared by different techniques. Furthermore, 2 '-alkynyl-substituted 2-phenylpyridines bearing terminal tert-butyl- and trimethylsilyl-groups are introduced as a new class of substrates for hydroboration. Successful hydroboration with either 9H-borabicyclo[3.3.1]-nonane (9H-BBN), dimesitylborane (Mes(2)B-H), or Piers' borane ((C6F5)(2)B-H, BPF-H) furnished new pi-extended boranes capable of forming intramolecular six- or seven-membered N -> B-heterocycles (tBuBBN, SiBPF), and, in the case of Mes(2)BH, formation of a sterically crowded styrylborane (SiBMes(2)) incapable of intramolecular N -> B-coordination was observed. All the boranes listed above except BMe2 have been structurally characterized, and a study of their electrochemical properties showed that the systematic variation of the substituents on boron allows for the incremental variation of the electron affinity of the phenylpyridine-model system over a total range of >0.7 eV between alkylboranes (BMe2, BBN) and B(CN)(NC). B(CN)(NC) shows the strongest N -> B-bond (approximate to 175 kJ mol(-1)), and highest electron-affinity observed so far, and is the first example of a borane bearing an isocyano-substituent on boron.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2019
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-391376 (URN)10.1039/c9dt01555h (DOI)000475742900042 ()31210241 (PubMedID)
Available from: 2019-09-03 Created: 2019-09-03 Last updated: 2019-09-03Bibliographically approved
Schraff, S., Sun, Y., Orthaber, A. & Pammer, F. (2019). Gold(I) Complexes of Fulvenyl-Functionalized Arylisocyanides. European Journal of Inorganic Chemistry (1), 42-50
Open this publication in new window or tab >>Gold(I) Complexes of Fulvenyl-Functionalized Arylisocyanides
2019 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, no 1, p. 42-50Article in journal (Refereed) Published
Abstract [en]

Gold(I) chloride complexes of arylisocyanides derived from 9-benzylidene-9H-fluorene (Flu), 5-benzylidene-1,2,3,4-tetraphenylcyclopentadiene (TPCp), and 5-benzylidene-5H-dibenzo[a,d]cycloheptene (Dbs) have been prepared. The crystal structures and electronic properties of the three complexes are discussed. UV/Vis data complemented by DFT calculations indicate that the gold(I) centers act as Lewis acids and increase the acceptor strength of the isocyano group. The metal center therefore indirectly affects the optical properties of the pi-conjugated ligands, but is not directly involved in electronic transitions.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2019
Keywords
Gold, Isocyanides, Fulvenes, Density functional calculations, Ligand effects
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-375875 (URN)10.1002/ejic.201801031 (DOI)000455968200007 ()
Funder
Swedish Research CouncilGerman Research Foundation (DFG)
Available from: 2019-02-04 Created: 2019-02-04 Last updated: 2019-02-04Bibliographically approved
Vanderkooy, A., Gupta, A. K., Foldes, T., Lindblad, S., Orthaber, A., Papai, I. & Erdélyi, M. (2019). Halogen Bonding Helicates Encompassing Iodonium Cations. Angewandte Chemie International Edition, 58(27), 9012-9016
Open this publication in new window or tab >>Halogen Bonding Helicates Encompassing Iodonium Cations
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2019 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 58, no 27, p. 9012-9016Article in journal (Refereed) Published
Abstract [en]

The first halonium-ion-based helices were designed and synthesized using oligo-aryl/pyridylene-ethynylene backbones that fold around reactive iodonium ions. Halogen bonding interactions stabilize the iodonium ions within the helices. Remarkably, the distance between two iodonium ions within a helix is shorter than the sum of their van der Waals radii. The helical conformations were characterized by X-ray crystallography in the solid state, by NMR spectroscopy in solution and corroborated by DFT calculations. The helical complexes possess potential synthetic utility, as demonstrated by their ability to induce iodocyclization of 4-penten-1-ol.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2019
Keywords
3c-4e bonds, halocyclization, halogen bonds, helices, iodonium ions
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-391952 (URN)10.1002/anie.201904817 (DOI)000476691200005 ()31074942 (PubMedID)
Funder
Swedish Research Council Formas, 2017-01173
Available from: 2019-08-28 Created: 2019-08-28 Last updated: 2019-08-28Bibliographically approved
Green, J. P., Wells, J. A. L. & Orthaber, A. (2019). Heavier pnictogens - treasures for optical electronic and reactivity tuning. Dalton Transactions, 48(14), 4460-4466
Open this publication in new window or tab >>Heavier pnictogens - treasures for optical electronic and reactivity tuning
2019 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 48, no 14, p. 4460-4466Article, review/survey (Refereed) Published
Abstract [en]

We highlight recent advances in organopnictogen chemistry contrasting the properties of lighter and heavier pnictogens. Exploring new bonding situations, discovering unprecedented reactivities and producing fascinating opto-electronic materials are some of the most prominent directions of current organopnicogen research. Expanding the chemical toolbox towards the heavier group 15 elements will continue to create new opportunities to tailor molecular properties for small molecule activation/reactivity and materials applications alike. This frontier article illustrates the elemental substitution approach in selected literature examples.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-384087 (URN)10.1039/c9dt00574a (DOI)000467173800033 ()30810143 (PubMedID)
Available from: 2019-06-19 Created: 2019-06-19 Last updated: 2019-06-19Bibliographically approved
Gudat, D., Orthaber, A., Slootweg, J. C. & Streubel, R. (2019). Phosphorus Special Issue in Honor of Koop Lammertsma and Edgar Niecke. European Journal of Inorganic Chemistry (11-12), 1437-1439
Open this publication in new window or tab >>Phosphorus Special Issue in Honor of Koop Lammertsma and Edgar Niecke
2019 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, no 11-12, p. 1437-1439Article in journal, Editorial material (Other academic) Published
Abstract [en]

Guest Editors Dietrich Gudat, Andreas Orthaber, Chris Slootweg, and Rainer Streubel report the increasing importance of phosphorus chemistry in Europe and beyond, summarizing the contributions in this special issue in honor of the 70th and 80th birthdays of Professors Koop Lammertsma and Edgar Niecke.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2019
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-382021 (URN)10.1002/ejic.201900192 (DOI)000462351000001 ()
Available from: 2019-04-23 Created: 2019-04-23 Last updated: 2019-04-23Bibliographically approved
Liu, T., Guo, M., Orthaber, A., Lomoth, R., Lundberg, M., Ott, S. & Hammarström, L. (2018). Accelerating proton-coupled electron transfer of metal hydrides in catalyst model reactions. Nature Chemistry, 10(8), 881-887
Open this publication in new window or tab >>Accelerating proton-coupled electron transfer of metal hydrides in catalyst model reactions
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2018 (English)In: Nature Chemistry, ISSN 1755-4330, E-ISSN 1755-4349, Vol. 10, no 8, p. 881-887Article in journal (Refereed) Published
Abstract [en]

Metal hydrides are key intermediates in catalytic proton reduction and dihydrogen oxidation. There is currently much interest in appending proton relays near the metal centre to accelerate catalysis by proton-coupled electron transfer (PCET). However, the elementary PCET steps and the role of the proton relays are still poorly understood, and direct kinetic studies of these processes are scarce. Here, we report a series of tungsten hydride complexes as proxy catalysts, with covalently attached pyridyl groups as proton acceptors. The rate of their PCET reaction with external oxidants is increased by several orders of magnitude compared to that of the analogous systems with external pyridine on account of facilitated proton transfer. Moreover, the mechanism of the PCET reaction is altered by the appended bases. A unique feature is that the reaction can be tuned to follow three distinct PCET mechanisms-electron-first, proton-first or a concerted reaction-with very different sensitivities to oxidant and base strength. Such knowledge is crucial for rational improvements of solar fuel catalysts.

National Category
Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-357209 (URN)10.1038/s41557-018-0076-x (DOI)000439420400015 ()30013192 (PubMedID)
Funder
Swedish Research Council, 2016-04271Knut and Alice Wallenberg Foundation, 2011.0067
Available from: 2018-08-13 Created: 2018-08-13 Last updated: 2019-01-04Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0001-5403-9902

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