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The cross-coupling reaction of organic electrophiles with organostannanes, traditionally known as the Stille reaction, has found renewed interest in the preparation of new organic materials such as conjugated polymers, organic semiconductors and photoactive molecules for use in organic photovoltaics. Moreover, a very recent field in which the Stille reaction has found successful application is that of the design and synthesis of new photosensitizers for dye-sensitized solar cells (DSSCs). DSSCs are considered a promising alternative for energy production from renewable sources. In such devices light harvesting is carried out by a dye which is generally a highly conjugated molecule. Due to the mild operating conditions and the high functional-group compatibility, the Stille reaction proved to be a powerful tool not only for the preparation of photosensitizers, but also to plan their chemical elaboration in order to tune and optimize their photophysical, electrochemical and photovoltaic properties. In this microreview some recent examples of the Stille reaction in the synthesis of organic dyes for DSSC are reported.

The use of the cyclopentadithiophene (cpdt) fragment to chemically link electron donor and acceptor groups has become a rather common procedure to design new organic dyes with enhanced light harvesting properties. The photo-to-current efficiencies obtained by sensitized solar cells with dyes incorporating the cpdt moiety are commonly improved with respect to other similar ?-fragments as separators. In many cases, the advantages of cpdt can be related to the larger extinction coefficients obtained. In this work we perform a detailed computational study of triarylamine-based organic dyes with the cyanoacrylic acid as the acceptor group and considering a variety of conjugated linkers with cpdt as the reference case. The influence of slightly different linkers and donor groups in the computed excitation energies and oscillator strengths is discussed by means of molecular geometries and frontier orbitals. The structural characteristics imposed by cpdt compared to similar conjugated bridges are responsible for its larger computed oscillator strengths. The insertion of an ethylene unit between the donor group and the linker systematically reduces the energy gap to the first excited singlet state and yields larger oscillator strengths of the optical transition. These results could be very helpful in the quest of new organic dyes with improved properties as sensitizers in Grätzel cells.