The preparation of fullerene complexes with metal tetraarylporphyrins in the presence of excess ferrocene (Cp(2)Fe) results in the formation of new solvent-free and multicomponent molecular crystals. New isomorphous complexes of C(60) with PyZnTPP (ZnTPP identical with zinc 5,10,15,20-tetraphenyl-21H,23H-porphyrinate) and PyCoTPP (CoTPP identical with cobalt(II) 5,10,15,20-tetraphenyl-21H,23H-porphyrinate) containing Cp(2)Fe and the isostructural C(70) complex with PyZnTPP have been prepared. The crystal structures of the new layered C(60) complexes CoTMPP x C(60) (obtained in the presence of Cp(2)Fe) and CoTMPP x 2C(60) x 3C(7)H(8) (obtained in the absence of Cp(2)Fe) have been described (CoTMPP identical with cobalt(II) 5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate). Cobalt atoms of the PyCoTPP and CoTMPP molecules are weakly coordinated to C(60) with Co...C(C(60)) distances in the 2.64-2.82 A range, whereas zinc atoms of PyZnTPP, as well as cobalt atoms of the CoTMPP molecules in the solvent-free phase, form only van der Waals contacts with fullerenes. Different packing arrangements in the crystals of fullerene-porphyrin complexes have been discussed.
Prototype solar cells made up of nanocrystalline anatase supported on a conducting glass and sensitized with two Ru 2+ complexes (cis-dithiocyanatobis(2,2′-bipyridine-4,4′-dicarboxylate)ruthenium(II), or red dye, and (4,4′,4′′-tricarboxy-2,2′:6′,2′′-terpyridine)ruthenium(II), or black dye) are characterized with out-of-plane X-ray diffraction, X-ray photoelectron spectroscopy, and Ti K-edge XAFS (XANES and EXAFS), as well as by powder X-ray diffraction of the pure dyes used for a coating of a TiO 2 layer. The data indicate, within the sensitivity limits of the methods applied, that the dyes most probably form (partial coverage) a monolayer at the surface of anatase nanoparticles. Coating with the dyes leads to a stronger distortion of the local environment of Ti atoms in anatase nanoparticles.
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