Semiconducting alkyl derivatives of 2,5-Bis(2,2′-bithiophene-5-yl)-1,3,4-thiadiazole - Effect of the substituent position on the spectroscopic, electrochemical, and structural properties

Ewa Kurach , Kamil Kotwica , J. Zapała , M. Knor , R. Nowakowski , D. Djurado , P. Toman , J. Pfleger , Małgorzata Zagórska , Adam Proń

Abstract

Unsubstituted 2,5-bis(2,2′-bithiophene-5-yl)-1,3,4-thiadiazole and four of its derivatives containing solubilizing octyl groups in different positions of the terminal thiophene ring were synthesized (3 new compounds and 2 already reported). Their UV–vis absorption and emission spectra turned out to be strongly dependent on the position of the substituent and showed significant bathochromic shifts of the dominant transition for compounds with the substituents attached to Cα of the terminal ring (λmax > 425 nm). A good correlation was found for the experimentally determined and theoretically calculated excitation energies employing the time-dependent Coulomb-attenuated hybrid exchange-correlation functional using the 6-31G* basis set (TD CAM-B3LYP/6-31G*). The calculations showed, in addition, that the alkyl substituents improved the planarity of the molecule and its aromaticity, and that they raised the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels (the latter to a lesser extent) via electron-donating effects. The only exception was the compound with the substituent attached to the inner Cβ position. In this case, the absorption band originating from the dominant transition was hypsochromically shifted in comparison to the corresponding transition in the unsubstituted compound, again in perfect agreement with the quantum chemical calculations, which predicted a less planar structure of this derivative. Theoretical calculations concerning the substituent-induced shifts of the HOMO and LUMO levels were found to be in good accordance with the ionization potential and the electron affinity changes determined by cyclic voltammetry, which showed the same trend. Thin films of the studied semiconductors deposited on SiO2/Si showed a highly anisotropic structure with molecules stacked almost perpendicular to the surface. Among all derivatives studied, the two compounds with substituents attached to the Cβ position formed ordered monolayers on highly oriented pyrolytic graphite in which molecular packing was much less dense than in 3D crystals. Preliminary investigations demonstrated that the synthesized new semiconductors could be used for fabrication of efficient light-emitting diodes. © 2013 American Chemical Society
Author Ewa Kurach (FC / CPCT)
Ewa Kurach,,
- Chair Of Polymer Chemistry And Technology
, Kamil Kotwica (FC / CPCT)
Kamil Kotwica,,
- Chair Of Polymer Chemistry And Technology
, J. Zapała - [Institute of Physical Chemistry of the Polish Academy of Sciences]
J. Zapała,,
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, M. Knor - [Institute of Physical Chemistry of the Polish Academy of Sciences]
M. Knor,,
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, R. Nowakowski - [Institute of Physical Chemistry of the Polish Academy of Sciences]
R. Nowakowski,,
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, D. Djurado - [Universite Grenoble Alpes (UGA)]
D. Djurado,,
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- Université Grenoble Alpes
, P. Toman - [Institute of Macromolecular Chemistry of the Academy of Sciences of the Czech Republic]
P. Toman,,
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, J. Pfleger - [Institute of Macromolecular Chemistry of the Academy of Sciences of the Czech Republic]
J. Pfleger,,
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, Małgorzata Zagórska (FC / CPCT)
Małgorzata Zagórska,,
- Chair Of Polymer Chemistry And Technology
, Adam Proń (FC / CPCT)
Adam Proń,,
- Chair Of Polymer Chemistry And Technology
Journal seriesThe Journal of Physical Chemistry Part C: Nanomaterials, Interfaces and Hard Matter, ISSN 1932-7447
Issue year2013
Vol117
No29
Pages15316-15326
Publication size in sheets0.5
Keywords in EnglishAnisotropic structure; Electron-donating effects; Exchange-correlation functionals; Highest occupied molecular orbital; Highly oriented pyrolytic graphite; Lowest unoccupied molecular orbital; Quantum chemical calculations; Theoretical calculations
ASJC Classification2508 Surfaces, Coatings and Films; 1606 Physical and Theoretical Chemistry; 2100 General Energy; 2504 Electronic, Optical and Magnetic Materials
DOIDOI:10.1021/jp4033832
URL http://pubs.acs.org/doi/abs/10.1021/jp4033832
Languageen angielski
File
jp4033832.pdf 1.65 MB
Score (nominal)35
Score sourcejournalList
ScoreMinisterial score = 35.0, 25-07-2020, ArticleFromJournal
Ministerial score (2013-2016) = 35.0, 25-07-2020, ArticleFromJournal
Publication indicators WoS Citations = 9; Scopus Citations = 11; GS Citations = 13.0; Scopus SNIP (Source Normalised Impact per Paper): 2013 = 1.432; WoS Impact Factor: 2013 = 4.835 (2) - 2013=5.241 (5)
Citation count*14 (2020-09-15)
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* presented citation count is obtained through Internet information analysis and it is close to the number calculated by the Publish or Perish system.
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