Unsymmetrical cyanine dyes are widely used in biomolecular detection due to their fluorogenic behavior, whereby fluorescence quantum yields can be very low in fluid solution but are significantly enhanced in conformationally restricted environments. Herein we describe a series of fluorinated analogues of the dye thiazole orange that exhibit improved fluorescence quantum yields and photostabilities. In addition, computational studies on these dyes revealed that twisting about the monomethine bridge beyond an interplanar angle of 60 leads to a dark state that decays nonradiatively to the ground state, accounting for the observed fluorogenic behavior. The effects of position and number of fluorine substituents correlate with both observed quantum yield and calculated activation energy for twisting beyond this critical angle.

Black dye (BD), isomer 1 ([RuII(H3-tctpy)(NCS)3]-1, where H3-tctpy = 4,4',4' '-tricarboxy-2,2':6,2' '-terpyridine) is known to be an excellent sensitizer for dye-sensitized solar cells and exhibits a very good near-IR photo response, compared to other ruthenium dyes. Because isothiocyanate is a linear ambidentate ligand, BD has three other linkage isomers, [Ru(H3-tctpy)(NCS)2(SCN)]-1, isomer 2 and 2', and [Ru(H3-tctpy))(SCN)3]-1, isomer 3. In this study, we have calculated the geometry of BD and its isomers by DFT. Further, we have analyzed the bonding in these isomers using NBO methods. TDDFT calculations combined with scalar relativistic zero-order regular approximations (SR-ZORA) have been carried out to simulate the absorption spectra. Calculations have been performed for the isomers both in vacuo and in solvent (ethanol). The inclusion of the solvent is found to be important to obtain spectra in good agreement with the experiment. The first absorption bands are dominated by the metal-to-ligand charge transfer (MLCT) and ligand-to-ligand charge transfer (LLCT).

The transport and recombination of electrons in dye-sensitized TiO2 solar cells were studied by analysis of the current and voltage response to a small square-wave light-intensity modulation. Solar cells were studied under working conditions by using potentiostatic and galvanostatic conditions. An increase in applied voltage, that is, from 0 V toward open-circuit voltage, was found to lead to faster electron transport at low light intensities, while it slowed transport at higher light intensities. This observation seems to be conflicting with the multiple trapping model with diffusive transport. An effective diffusion length at the maximum power point was calculated, and it was shown that it decreases with increasing light intensity.

Narukuni Hirata, Jessica E. Kroeze, Taiho Park, David Jones, Saif A. Haque, Andrew B. Holmes and James R. Durrant

Emi Horiguchi, Kazuko Shirai, Masaru Matsuoka, and Masaki Matsui

M. C. Zerner, C. Reidlinger, W. M. F. Fabian, and H. Junek

Jiabo Li, Christopher J. Cramer *, Donald G. Truhlar