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Thiocyanate-free Ru(II) complexes as photosensitizers for dye-sensitized solar cells (DSSCs) are presented. These classes of complexes have gained in recent times increasing interest due to their more favorable long-term stability compared to conventional thiocyanate-based complexes such as benchmark dyes N719 and Z907. Here two classes of thiocyanate-free ruthenium(II) complexes have been reviewed: (a) bis-bipyridyl complexes bearing an ancillary cyclometallated bidentate ligand; (b) bipyridyl complexes bearing non-cyclometallated bidentate ancillary ligands. The article briefly outlines design strategies and optical and photovoltaic properties of these two families of ruthenium dyes. Although their photovoltaic performances is not as high as that of N719, recent increasing efforts by many research groups have allowed to achieve favorable light harvesting abilities, device photocurrents, and top-ranked power conversion efficiencies in combination with superior long-term stabilities, paving the way to efficient solar devices endowed with long-term chemical and thermal stability for viable large-scale commercialization of DSSCs.

We report on a series of novel homologous push-pull compounds, in which identical donor (a dimethylamino) and acceptor (a malonate ester) functionalities endcap crescent PPV fragments, bearing, respectively, 1, 2 and 3 p-phenylenevinylene units in direct linear conjugation (compounds 7-9). The three compounds exhibit striking differences in their linear and nonlinear optical properties. The shorter compound 7 exhibits aggregation-induced emission with a strong luminescence in the solid state (blue emission, photoluminescence quantum yield 38%), and it is nonemissive in solution; the more extended conjugated systems 8 and 9 show classical aggregation-caused quenching in the solid state, while high quantum yield photoluminescence (21 and 93% in toluene) is restored in diluted solutions, through mechanisms involving intramolecular charge transfer in the excited states. EFISH measurements in solutions demonstrate a strong solvent and concentration dependence. As rationalized with the aid of molecular modelling, compounds 8 and, more markedly, 9 aggregate in stable centrosymmetric dimers in solution. © 2013 the Owner Societies.

Two families of thiophene-based 2-arylpyridines, in which aryl is phenyl and 2,4-difluorophenyl, have been developed. The pyridine ring of the new compounds is substituted at the 4-position with π-conjugated electron-rich and electron-poor thiophene-based fragments to tune the optical and energetic properties. The high-yielding synthetic access, which consists of two sequential Suzuki coupling reactions, the first of which is completely regioselective, is of wide applicability and allows access to a large variety of derivatives. The absorption/emission and redox features, as well as the HOMO and LUMO energy levels, have been investigated; the results show that the optical and electronic properties can be tuned over a broad range. The diversity of the characteristics may be effectively exploited by using the thiophene-substituted 2-arylpyridines as ligands in cyclometalated sensitizers for dye-sensitized solar cells and other optoelectronic applications. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.