Modification of optoelectronic properties of conjugated oligomers due to donor/acceptor functionalization: DFT study

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• 作者：Andriy Zhugayevych^a ; ^{a.zhugayevych@skoltech.ru} ; Olena Postupna^b ; Hsing-Lin Wang^b ; Sergei Tretiak^b ; ^a
• 关键词：Functionalized p-phenylene vinylene ; Distyrylbenzene ; Molecular descriptor ; Push&ndash ; pull functionalization ; Structure&ndash ; property relationship
• 刊名：Chemical Physics
• 出版年：2016
• 出版时间：20 December 2016
• 年：2016
• 卷：481
• 期：Complete
• 页码：133-143
• 全文大小：1338 K
• 卷排序：481

文摘

A comprehensive DFT study of a set of oligo(p-phenylene vinylene) molecules is performed to understand the structural and electronic changes upon functionalization. These changes are rationalized within a model considering frontier molecular orbitals of the ππ-conjugated system and σσ-bonding orbital by which the functional group is attached to the host molecule. Two simple scalar quantum chemical descriptors are shown to correlate with optoelectronic properties of the functionalized molecule: the electronegativity and the relative electric dipole moment of the smallest ππ-closed shell subsystem containing the functional group and the terminal segment of the host molecule (phenyl). Both descriptors correlate linearly with the empirical Hammett σpσp constant for a set of 24 functional groups. Comparison with available experimental data on UV–vis absorption and cyclic voltammetry is made. Observed structural changes reflect changes in the electronic density.