Geometric and chelation influences on the electronic structure and optical properties of tetra(carboxylic acid)phenyleneethynylene dyes

Asher Berlin, Chad Risko, Mark A. Ratner

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A quantum-chemical study on the consequences of geometric modification and chelation on the electronic structure and optical properties of a tetra(carboxylic acid)phenyleneethynylene dye, of interest for chemical sensing applications, is presented. Rotation within the central biphenylene and complexation with divalent metal ions -in particular Cu2+ -lead to notable changes in the absorption and emission profiles. Calculations at both the density functional theory (DFT) and Hartree-Fock (HF) levels are used to evaluate geometric potential energy surfaces for rotation within the central biphenylene unit; HF coupled with configuration interaction singles (HF-CIS) is used to investigate the first excited state of the dye. Time-dependent DFT (TDDFT) calculations are employed to assess changes in optical absorption and fluorescence as a function of geometry and chelation.

Original languageEnglish
Pages (from-to)4202-4208
Number of pages7
JournalJournal of Physical Chemistry A
Issue number18
Publication statusPublished - May 8 2008


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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