Zhuravlyov S. Complex compounds of lanthanides with asymmetrical substituents tetrapyrroles of porphyrins and porphyrazines series: synthesis, structure and spectral-luminescent properties

Object of investigation: The complexes of lanthanides (ytterbium, erbium, lutecium) with asymmetrically substituted porphyrins and porphyrazins. Aim of investigation: synthesis, establishment of composition and structure of the new complexes of lanthanides with asymmetrically substituted porphyrins and porphyrazins. Methods of investigation and instruments: element analysis, IR-, UV-, NMR- 1H- and luminescent (stationary and kinetic) spectroscopy, mass-spectrometry. Determination and analysis of structural features of the studied compaund was conducted by methods of molecular mechanics. Theoretical and practical results, novelty: The 72 lantanide complexes from 29 asymmetrically substituted cyclic tetrapirroles (porphyrins and porphyrazins) are synthesized . Absolute majority from these compounds (61) was synthesized first. With bringing in of methods of molecular mechanics, calculations of the charge distributing on co-ordinating-active atoms the systematic study of intercommunication of composition, structure and spectro-luminescence properties of complexes of lantanides with cyclic tetrapirroles was first conducted. Effective 4f-luminescence of ytterbium and erbium is set in all studied complexes. On the example of complexes with asymmetrically substituted derivatives of meso-tetraphenylporphyrins, containing substitutes in meso- and ?-positions, was rotined that on intensity of luminescence both donor-acceptor properties of deputies and their location in a phenylic ring has an influence. The new types of f-d-geterobinuclear complexes got with porphyrins, substituted ?-diketones fragments, and with 2,3-ditiolatoporphyrazin. It is rotined that ions of Cu2+, Ni2+ and Zn2+ are quencher of 4f-luminescence in these complexes, and ions of Pd2+- sensitizers. The complexes of lutecium with a porphyrin-chalcones and porphyrin-pirazoles are first offered as perspective photosensitizers in photodynamic therapy of tumours. Field of application: inorganic chemistry.