CONTENTS

The discovery and characterization of the first example of a bis-cadmium tris-phthalocyanine triple-decker sandwich complex is reviewed. The scope for obtaining further examples of this new class of complex bearing different ring substituents is also described. A spectroscopic and electrochemical study on the monomeric precursors revealed the mode of formation of the triple-decker complexes. From the results of cross experiments, it is proposed that the triple-decker structures are formed by self-assembly processes and that they can disassemble and reassemble in the solution phase. Preliminary measurements have identified ring substitution patterns that lead to higher oligomers. Supplementary Material

This review aims to summarise the development of the synthesis of reduced derivatives of tetraazaporphine such as tetraazachlorin, tetraazabacteriochlorin and tetraazaisobacteriochlorin. The synthesis of these compounds known to date is based on three alternate strategies, namely, catalytic hydrogenation of tetraazaporphines, mixed condensation of the precursors with different hydrogenation levels and modification of tetraazaporphine macrocycles through β–β addition reactions.

We report here on the synthesis, isolation and characterization of unsymmetrically substituted subphthalocyanines, obtained from the mixed condensation of 4,5-substituted phthalonitriles and/or 4-substituted phthalonitriles in the presence of BCl₃. Supplementary Material

Conjugate molecule of N-confused tetraphenylporphyrin and azobenzene was synthesized and characterized in detail, in which the moderate red-shift is induced by interaction between porphyrin π-system and azobenzene π-system. This effect can be negated upon protonation at the peripheral nitrogen atom.

Condensation reaction of 2-amino-3-[(3-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile with the series of diketones led to novel dinitriles, of which 2-(2,5-dimethyl-1H-pyrrol-1-yl)-3-[methyl (3-pyridylmethyl) amino]-2(Z)-butene-1,4-dinitrile was successfully utilized in the Linstead macrocyclization towards symmetrical and unsymmetrical porphyrazines. Supplementary Material

The synthesis and properties of substituted triphenylenophthalocyanines are described where the benzene rings of phthalocyanines are replaced by triphenylene units. The resulting materials are macrodiscotic in nature and show red-shifted absorption spectra and columnar mesophase behavior over a wide temperature range.

New glycochlorins are formed from the reaction of carbohydrate substituted α-diazoacetates with meso-tetrakis(pentafluorophenyl)porphyrinatozinc(II), catalysed by CuCl. The new compounds are better singlet oxygen generators than methylene blue.

gem-dimethylisocorrole gave four-coordinate Ni(II) and Cu(II) complexes, five-coordinate (chloro)Fe(III) and (chloro)Mn(III) complexes, and six-coordinate (chloro)(pyridinato)Rh(III) complex in moderate to good yields. The dinuclear complexes such as μ-oxo-diiron(III) complex and (tetracarbonyl)dirhodium(I) complex were also prepared. The structures of these mononuclear and dinuclear complexes were determined by X-ray crystallography.

We report the synthesis and characterization of two novel tetrasubstituted Zn phthalocyanines, bearing bulky alkylaryloxy substituents into the so-called peripheral (locations 2,3,9,10,16,17,23,24) and non-peripheral (locations 1,4,8,11,15,18,22,25) positions, and a new trinitrofluorenonepyridine derivative (TNFPy). The non-peripheral substituted ZnPc has been isolated as a single regioisomer by column chromatography. ¹H NMR experiments have confirmed the formation of 1:1 complexes, being the system non-peripheral ZnPc-TNFPy the one with the larger value of binding constant (K = 1.4 ± 0.2 × 10⁵ M^-1), which suggests a better accessibility to the metallic center than for the system peripheral ZnPc-TNFPy (K = 4.1 ± 0.4 × 10³ M^-1). Supplementary Material

Novel heteropentameric porphyrins-pyrene arrays, in which four meso-tetraphenyl porphyrins were linked to the center unit of pyrene by four acetylenyl bonds, were designed and synthesized. The newly synthesized heteropentameric compounds have been characterized by a wide range of spectroscopic methods. The third-order nonlinear optical (NLO) properties of both the metal free and zinc compounds of the three-dimensional arrays were investigated by Z-scan experiments in CHCl₃ solution, showing enhanced NLO properties compared with that of the porphyrin and pyrene monomers. Supplementary Material

We have found a new regioselective one-pot synthetic route for preparation of heteroleptic (porphyrinato)(phthalocyaninato) triple-decker complexes Ln₂[An₄P]₂[(15C5)₄Pc]. The second product of the synthesis is heteroleptic double-decker complex, which does not complicate the purification procedure. The found method is presumed to be general for early lanthanide (porphyrinato)(phthalocyaninates).

World Scientific is a Member of CrossRef

Copyright © 2012 World Scientific Publishing Co. All rights reserved.