Novel pyridine-substituted subphthalocyanines were prepared for an additional harvesting of a green spectral region of the solar light spectrum for zinc phthalocyanine-based dye-sensitized solar cells. These compounds can bind with the central metal of zinc phthalocyanines to form the corresponding supramolecular complexes as monitored by the absorption and fluorescence spectral changes. The stability constants of these complexes were altered by the number and position of pyridine units in the pyridine-substituted subphthalocyanines. On the basis of fluorescence titration study, the complexes efficiently transfer energy from the subphthalocyanine to zinc phthalocyanine. The solar cells using TiO electrodes stained with the supramolecular complexes, composed of zinc phthalocyanine sensitizer and pyridine-substituted subphthalocyanines, showed panchromatic responses, and the photocurrent generation in the range of 500-600 nm is attributed to the efficient Förster resonance energy transfer from subphthalocyanine to zinc phthalocyanine on the TiO surface.

Condensation of 1,8-diamino-3,6-dichlorocarbazole with aseries of disubstituted 1,3-diiminoisoindolines,followed by treatment with BF 3 ·OEt 2 led to the formation of the corresponding core-expanded boron(III) subphthalocyanine analogues.T hese air-stable p-conjugated boron(III) carbazosubphthalocyanines possess two boron-containing seven-membered-ring units and a16p-electron skeleton, and represent the first examples of antiaromatic boron(III) subphthalocyanine analogues as supported by spectroscopic and theoretical studies.T he molecular structure of one of these compounds was unambiguously determined by single-crystal X-ray diffraction analysis.I nc ontrast to typical boron(III) subphthalocyanines,whichadopt acone-shaped structure,the p skeleton of this compound is almost planar.

Two three-dimensional (3D) network polymers (1 and 2), in which zinc­(II) or cobalt­(II) phthalocyanines were interconnected with twisted 9,9′-spirobifluorene linkers, were synthesized in order to investigate their performance as heterogeneous catalysts for thiol oxidations. From the spectroscopic analyses of two dimers (3 and 4) as component units of the network polymers, 3 connected with a short linker revealed electronic interaction between the two phthalocyanine units. Micrometer-sized polymer particles were formed due to the condensation of the twisted 9,9′-spirobifluorene linkers in the presence of zinc or cobalt ions. The dispersed solutions of 1 and 2 had sharp Q-bands, indicating the prevention of stacking among phthalocyanine moieties within the polymers. Powdered X-ray diffraction pattern and N2 adsorption–desorption analyses suggested that 1 created small and rigid cavities as compared with 2 through the regular spatially arrangement of the phthalocyanine moieties in the 3D networks. The photocatalytic and catalytic activities of 1 and 2 for thiol oxidations using molecular oxygen were examined. We found that the catalytic activity of 1 was higher than that of 2 having larger cavities.

Condensation of 4,5-bis(4-tert-butyl-2,6dimethylphenoxy)phthalonitrile with 2,9-diamino-1,10-phenanthroline in the presence of M(OAc) 2 (M = Ni, Pd, Zn) afforded a series of phenanthroline-fused phthalocyanine analogues with a 16 π-electron skeleton. While the arrangement of elements along the inner perimeter of these macrocycles is the same as that of the hitherto reported trivalent corroles, they represent the first example of porphyrinoids possessing a monovalent corrole inner perimeter and nonaromatic characteristics as revealed by their spectroscopic data and theoretical studies.

A series of metal-free and metallo-diazaporphyrin analogues embedded with a 1,10-phenanthroline unit were synthesized and characterized. The molecular structure of the Ni(II) complex determined by single-crystal X-ray diffraction analysis confirmed its monocationic character in which the metal center adopts a typical square planar geometry binding with the pyrrole and phenanthroline nitrogen atoms. The spectroscopic and electrochemical studies, as well as molecular orbital calculations suggested that the metal complexes can be classified as 4nπ non-aromatic compounds.