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.

A novel synthetic strategy for low-symmetry phthalocyanines has been developed, which involves the basepromoted cyclization of a preconnected trisphthalonitrile and a free phthalonitrile in the presence of a metal template. By using this [3 + 1] mixed cyclization approach, a series of zinc(II) phthalocyanine derivatives have been synthesized in up to 12% yields, including a very rare ABCD-type phthalocyanine and an amphiphilic ABACtype analogue that can self-assemble in aqueous media, forming stable spherical nanoparticles.

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.

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.