Photochemical reactions of charge-transfer complexes. The irradiation of the charge-transfer complexes between 1,4-, 1,5-, and 2,3-dimethoxynaphthalenes and 1,2-dicyanoethylenes

Abstract

The first part of this paper describes the experimental search for a donor which would complex preferentially one of the isomers of 1,2-dicyanoethylene. This involved measuring the association constants (KcDA) of the charge-transfer (ct) complexes of several dimethoxynaphthalenes (DMN) with maleonitrile (MN) and fumaronitrile (FN). From the measured KcDA, we found that MN complexes more strongly than FN with 1,4- and 1,5-DMN but that FN complexes more strongly with 2,3-DMN than does MN. These results are explained in terms of more than one favourable geometry for the ct complexes, since the donors are relatively large compared to the acceptors.Irradiation of the ct complexes between 1,4-, 1,5-, or 2,3-DMN and 1,2-dicyanoethylene led to isomerization of the olefins. The photostationary state depends on the absorption spectra of the ct complexes formed between the donor and the isomeric olefins. From spectroscopic and photo-CIDNP studies, we find evidence that the isomerization in polar solvents takes place via the triplet state of the olefin. The triplet is formed from the radical ion pair resulting after excitation of the ct complex.