RESUMO
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 CâC 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 µß values (except for thiobarbiturate derivatives).