Metal (M = Cr, Mo, W, Re) carbonyl complexes with porphyrin and carborane isocyanide ligands: light-induced oxidation and carbon oxide release for antitumor efficacy.

The tetrapyrrolic macrocycle as a scaffold for various chemical modifications provides broad opportunities for the preparation of complex multifunctional conjugates suitable for binary antitumor therapies. Typically, illumination with monochromatic light triggers the photochemical generation of reactive oxygen species (ROS) (photodynamic effect). However, more therapeutically valuable effects can be achieved upon photoactivation of tetrapyrrole derivatives.

Synthesis of new representatives of AB-type carboranylporphyrins based on -tetra(pentafluorophenyl)porphyrin transformations.

A carboranylporphyrin of AB-type bearing a single pentafluorophenyl ring was prepared through the regioselective nucleophilic aromatic substitution reaction of the -fluorine atoms in 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin with 9-mercapto--carborane. The reaction of this porphyrin with sodium azide led to the selective substitution of the -fluorine atom in the pentafluorophenyl substituent with an azide functionality which upon reduction with SnCl resulted in the formation of the corresponding porphyrin with an amino group. Pentafluorophenyl-substituted AB-porphyrins were studied and transformed to thiol and amino-substituted compounds allowing for the preparation of porphyrins with different reactive groups such as hydroxy and amino derivatives capable for further functionalization and conjugation of these porphyrins to other substrates.

Multicomponent Molecular Systems Based on Porphyrins, 1,3,5-Triazine and Carboranes: Synthesis and Characterization.

2,4,6-Trichloro-1,3,5-triazine (cyanuric chloride) is an excellent coupling reagent for the preparation of highly structured multifunctional molecules. Three component systems based on porphyrin, cyanuric chloride and carborane clusters were prepared by a one-pot stepwise amination of cyanuric chloride with 5-(4-aminophenyl)-10,15,20-triphenylporphyrin, followed by replacement of the remaining chlorine atoms with carborane - or -nucleophiles. Some variants of 1,3,5-triazine derivatives containing porphyrin, carborane and residues of biologically active compounds such as maleimide, glycine methyl ester as well as thioglycolic acid, mercaptoethanol and hexafluoroisopropanol were also prepared.