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Authors
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Raychev, D. ; Guskova, O. ; Seifert, G. ; Sommer, J.-U.
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Title
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Conformational and electronic properties of small benzothiadiazole-cored oligomers with aryl flanking units: Thiophene versus furan
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Date
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25.10.2016
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Number
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50941
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Abstract
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Symmetrical benzothiadiazole-cored (BTZ) oligomers with aromatic flanks are widely used in experiments as structural blocks for organic electronic materials. Along with chemical composition, the molecular conformation plays a crucial role in crystal packing/self-assembly of these building blocks in thin films. In this study, we perform an extensive theoretical comparison of conformational preferences, electronic and optical properties of small p-conjugated molecules having BTZ central unit symmetrically decorated with thiophene (Th) or furan (Fu) rings using DFT calculations. In addition to the conformational screening of small molecules, the torsion potentials of the internal rotation and the energetics of weak intramolecular S·N, O·N, O·H and N·H nonbonded interactions stabilizing certain conformations are evaluated. The conformational properties of –[BTZ-Fu]n– and –[BTZ-Th]n– chains are predicted applying the hindered rotation model. Our calculation shows that substitution of one atom, here sulphur by oxygen, leads to huge stiffening of the resulting polymer as estimated by the Kuhn length based on the rotational isomeric model. On the other hand, the calculation of the band gaps and the UV–vis spectra shows that the electronic and optical properties of both compounds are almost identical. This offers the possibility to decouple the intramolecular electronic properties from the intermolecular arrangement and the morphology of the materials since the latter properties are sensitive to the local stiffness of oligomers and polymers.
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Publisher
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Computational Materials Science
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Wikidata
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Citation
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Computational Materials Science 126 (2016) 287-298
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DOI
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https://doi.org/10.1016/j.commatsci.2016.09.044
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Tags
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dft benzothiadiazole conformer noncovalent interactions kuhn segment ribbon-like polymer
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