Comparison of CC triple and double bonds as spacers in push-pull chromophores

Frank, BB, Laporta, PR, Breiten, B, Kuzyk, MC, Jarowski, PD, Schweizer, WB, Seiler, P, Biaggio, I, Boudon, C, Gisselbrecht, J-P and Diederich, F (2011) Comparison of CC triple and double bonds as spacers in push-pull chromophores European Journal of Organic Chemistry, 2011 (23). pp. 4307-4317.

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Abstract

We report the synthesis and properties of two series of homologous donor–acceptor (D–A) chromophores in which N,N-dimethylanilino (DMA) or N,N-dihexylanilino (DHA) donors and dicyanovinyl acceptors are separated by up to four C≡C triple-bond spacers or up to three C=C double-bond spacers. The intramolecular charge-transfer (CT) interactions of the new D–A oligoynes and the known all-trans D–A oligoenes were investigated by X-ray crystallography, electrochemistry, UV/Vis spectroscopy, and theoretical calculations. In both series, the optical and electrochemical HOMO–LUMO gaps decrease with increasing spacer length. The HOMO–LUMO gaps for the D–A oligoynes and oligoenes with a given spacer length are nearly identical. The effect of the spacer length was found to level-off for spacers with more than six carbon atoms. The third-order optical nonlinearity of both series of molecules was determined by measuring the rotational averages of the third-order polarizabilities rot by degenerate four-wave mixing.

Item Type:	Article
Authors :	Authors Email ORCID Frank, BB UNSPECIFIED UNSPECIFIED Laporta, PR UNSPECIFIED UNSPECIFIED Breiten, B UNSPECIFIED UNSPECIFIED Kuzyk, MC UNSPECIFIED UNSPECIFIED Jarowski, PD UNSPECIFIED UNSPECIFIED Schweizer, WB UNSPECIFIED UNSPECIFIED Seiler, P UNSPECIFIED UNSPECIFIED Biaggio, I UNSPECIFIED UNSPECIFIED Boudon, C UNSPECIFIED UNSPECIFIED Gisselbrecht, J-P UNSPECIFIED UNSPECIFIED Diederich, F UNSPECIFIED UNSPECIFIED
Date :	2011
Identification Number :	https://doi.org/10.1002/ejoc.201100378
Depositing User :	Symplectic Elements
Date Deposited :	28 Mar 2017 13:10
Last Modified :	28 Mar 2017 13:10
URI:	http://epubs.surrey.ac.uk/id/eprint/805650

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