Twisted One-Dimensional Charge Transfer and Related Y-Shaped Chromophores with a 4H-Pyranylidene Donor: Synthesis and Optical Properties.

Abstract

Three series of push–pull derivatives bearing 4H-pyranylidene as electron donor group and a variety of acceptors were designed. On one hand, one-dimensional chromophores with a thiophene ring (series 1H) or 5-dimethylaminothiophene moiety (series 1N) as an auxiliary donor, non-coplanar with the π-conjugated system, were synthesized. On the other hand, related two-dimensional (2D) Y-shaped chromophores (series 2) were also prepared to compare how the diverse architectures affect the electrochemical, linear, and second-order nonlinear optical (NLO) properties. The presence of the 5-dimethylaminothiophene moiety in the exocyclic C=C bond of the pyranylidene unit gives rise to oxidation potentials rarely low, and the protonation (with an excess of trifluoroacetic acid) of its derivatives results in the apparition of a new blue-shifted band in the UV–visible spectra. The analysis of the properties of derivatives with and without the additional thiophene ring shows that this auxiliary donor leads to a higher NLO response, accompanied by an enhanced transparency. Y-shaped chromophores of series 2 present a blue-shifted absorption, higher molar extinction coefficients, and higher Eox values compared to their linear twisted counterparts. As concerns NLO properties, 2D Y-shaped architecture gives rise to somewhat lower μβ values (except for thiobarbiturate derivatives).