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Donor‐Substituted Cyanoethynylethenes: π‐Conjugation and Band‐Gap Tuning in Strong Charge‐Transfer Chromophores
Author(s) -
Moonen Nicolle N. P.,
Pomerantz William C.,
Gist Robin,
Boudon Corinne,
Gisselbrecht JeanPaul,
Kawai Tsuyoshi,
Kishioka Atsushi,
Gross Maurice,
Irie Masahiro,
Diederich François
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200500082
Subject(s) - chromophore , intramolecular force , electrochemistry , molecule , acceptor , chemistry , photochemistry , ground state , silylation , spectroscopy , electron transfer , band gap , crystallography , materials science , stereochemistry , catalysis , organic chemistry , optoelectronics , atomic physics , physics , electrode , quantum mechanics , condensed matter physics
An extensive series of silyl‐protected cyanoethynylethenes (CEEs) and N , N ‐dimethylanilino donor‐substituted CEEs have been synthesized. More extended chromophores were constructed by selective silyl deprotection and subsequent oxidative acetylenic coupling. The strong electron‐accepting nature of the CEEs was revealed by a combination of 13 C NMR spectroscopic and electrochemistry measurements. Donor‐substituted CEEs display strong intramolecular charge‐transfer (CT) character, resulting in intense, bathochromically shifted CT bands in the UV/Vis spectrum. Their structural diversity establishes them as suitable models for the study of π‐conjugation and band gap tuning in strong charge‐transfer chromophores. The extent of π‐conjugation in the donor‐substituted CEEs was investigated by a combination of ground‐state techniques, such as X‐ray crystallography, electrochemistry, B3 LYP calculations, and NMR spectroscopy. The comparison of these ground‐state results with the features observed in the UV/Vis spectra reveals that—contrary to expectations—more extensive π‐conjugation can lead to larger band gaps in molecules with strong donor and acceptor moieties.