Journal of Porphyrins and Phthalocyanines

Metallophthalocyanine complexes and related compounds play an important role in many advanced applications and modern technologies mostly by virtue of their characteristic optical absorption and high chemical stability. As a class of materials made well-known by their vivid and fast colors, it is expected that metallophthalocyanines and analogues, e.g. naphthalocyanines, are going to keep their role with the increasing use of natural and artificial light in the technologies of the future. In the present review some relevant properties of phthalocyanines and related macrocycles for technological applications are analyzed. In particular the electrical conductivity and photoconductivity as well as some nonlinear optical properties (mostly optical limiting), of phthalocyanines and related compounds are discussed.

Contemporary methods for the modification of porphyrins are presented. In association with the Third International Conference on Porphyrins and Phthalocyanines (ICPP-3) a survey of current method developments and reactivity studies is made. The review focuses on synthetic transformations of porphyrins currently in use for various applications and on functional group transformations. A brief survey of important developments covers selectively the literature from late 2001 to early 2004.

Strategies for increasing the affinity of photodynamic sensitisers for specific tissues, cells and organisms are reviewed. Biological outcomes are evaluated and therapeutic potential assessed.

Recent advances in electron transfer chemistry of supramolecular electron donor-acceptor assemblies – containing porphyrins and metalloporphyrins – in connection with ICPP-3 are reviewed briefly by focusing on aspects of electron and energy transfer reactions.

The nonlinear optical (NLO) properties of lanthanide bisphthalocyanine (Lu(TBPc)Pc), including first hyperpolarizability, second hyperpolarizability and reverse saturable absorption (RSA), have been investigated. Furthermore, Lu(TBPc)Pc has also been applied for optical switch based on its RSA performance.

Oxidative cleavage of synthetic 5-phenyl protohemin IX in pyridine solution in the presence of ascorbic acid (coupled oxidation), followed by esterification of the products with boron trifluoride-methanol rendered mainly three isomeric biliverdins. These were identified by MS and 1D and 2D ¹H NMR as 15-phenyl biliverdin IXβ (1), 10-phenyl biliverdin IXγ (2) and 5-phenyl biliverdin IXδ (3) dimethyl esters. The fact that biliverdin IXα dimethyl ester derivative is not obtained indicates that oxidation fails to occur in the α-meso-carbon bearing the phenyl group.

An ab initio study of a promising nido-carboranylporphyrin for the boron neutron capture therapy of tumors, and of its closo precursor is reported. Base-induced deboronation of neutral ZnDCP, believed to exist as a mixture of 3 stereoisomers, produces the tetraanionic ZnDCP^4- as a complex mixture of isomers. ¹H NMR data and ab initio calculations support these findings. The position of the axial pyridine ligand in ZnDCP^4- and the orientation of the endo hydrogen atoms on the open faces of the nido-carborane cages significantly influence the total energy of the ZnDCP^4- structures. It is suggested that the "cocktail" of isomers possibly enhances the biological activity of tetra(nido-carboranyl)porphyrins, such as ZnDCP^4-.