title: Aromatic/proaromatic donors in 2-dicyanomethylenethiazole merocyanines: from neutral to strongly zwitterionic nonlinear optical chromophores.
abstract: Push-pull compounds, in which a proaromatic electron donor is conjugated to a 2-dicyanomethylenethiazole acceptor, have been prepared, and their properties compared to those of model compounds featuring an aromatic donor. A combined experimental (X-ray diffraction, (1) H NMR, IR, Raman, UV/Vis, nonlinear optical (NLO) measurements) and theoretical study reveals that structural and solvent effects determine the ground-state polarisation of these merocyanines: whereas 4H-pyran-4-ylidene- and 4-pyridylidene-containing compounds are zwitterionic and 1,3-dithiol-2-ylidene derivatives are close to the cyanine limit, anilino-derived merocyanines are essentially neutral. This very large range of intramolecular charge transfer (ICT) gives rise to efficient second-order NLO chromophores with μβ values ranging from strongly negative to strongly positive. In particular, pyranylidene derivatives are unusual in that they show an increase in the degree of ICT on lengthening the π-spacer, a feature that lies behind the very large negative μβ values they display. The linking of the formally quinoidal 2-dicyanomethylenethiazole moiety to proaromatic donors seems a promising approach towards the optimisation of zwitterionic NLO chromophores.
authors.affiliation: Departamento de Química Orgánica, ICMA, Universidad de Zaragoza-CSIC, Pedro Cerbuna 12, 50009 Zaragoza, Spain.
authors.forename: Raquel
authors.initials: R
authors.lastname: Andreu
authors.forename: Elena
authors.initials: E
authors.lastname: Galán
authors.forename: Jesús
authors.initials: J
authors.lastname: Orduna
authors.forename: Belén
authors.initials: B
authors.lastname: Villacampa
authors.forename: Raquel
authors.initials: R
authors.lastname: Alicante
authors.forename: Juan T López
authors.initials: JT
authors.lastname: Navarrete
authors.forename: Juan
authors.initials: J
authors.lastname: Casado
authors.forename: Javier
authors.initials: J
authors.lastname: Garín