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Lone-Pair Delocalization Effects within Electron Donor Molecules: The Case of Triphenylamine and Its Thiophene-Analog
Uppsala Univ, Dept Phys & Astron, Box 516, SE-75120 Uppsala, Sweden..
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology.
Sincrotrone Trieste, CNR, ISM, I-34149 Trieste, Basovizza, Italy..
CNR, ISM, I-85050 Potenza, Italy..
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2018 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 122, no 31, p. 17706-17717Article in journal (Refereed) Published
Abstract [en]

Triphenylamine (TPA) and its thiophene-analog, N,N-diphenyl-2-thiophenamine (DPTA), are both well-known as electron-donating molecules implemented in optoelectronic devices such as organic solar cells and LEDs. Comprehensive valence and core level photoelectron spectroscopy, as well as near edge X-ray absorption spectroscopy (NEXAFS), measurements have been performed on gas phase TPA and DPTA. The experimental results have been compared to density functional theory calculations, providing a detailed description of the molecular electronic structure. Specifically, the C 1s photoelectron lines of both TPA and DPTA were resolved in the different C atom contributions and their binding energies explained as the result of two counter-acting effects: (1) the electronegativity of the nitrogen atom (and sulfur atom in DPTA) and (2) the the N (and S in DPTA) lone-pair electrons. In addition, the C K-edge NEXAFS spectrum of DPTA reveals that the lowest unoccupied molecular orbital (LUMO) energy position is affected differently if the core hole site is on the phenyl compared to the thiophene ring. The electron-donating properties of these two molecules are largely explained by the significant contribution of the N lone-pair electrons (p(z)) to the highest occupied molecular orbital. The contribution to the LUMO and to the empty density of states of the sulfur of the thiophene ring in DPTA explains the better performance of donor-pi-acceptor molecules containing this moiety and implemented in photoenergy conversion devices.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC , 2018. Vol. 122, no 31, p. 17706-17717
National Category
Theoretical Chemistry
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URN: urn:nbn:se:kth:diva-234182DOI: 10.1021/acs.jpcc.8b06475ISI: 000441484600014Scopus ID: 2-s2.0-85049934390OAI: oai:DiVA.org:kth-234182DiVA, id: diva2:1252937
Note

QC 20181003

Available from: 2018-10-03 Created: 2018-10-03 Last updated: 2018-10-03Bibliographically approved

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