In recent decade, we have been engaged with the development of procedures of electrochemical synthesis of thin-film nanopolymers on the basis of transition metal complexes. Such supramolecular-organized structures show electric conductivity, are photoelectrochemically active, and can be used in information technologies and photoelectric devices due to their ability to the photo-and electro-induced charge transfer processes [1]. In addition, the analogous molecular system can be used to solve the problems of the solar energy accumulation and conversion, of ecological safety (electrocatalysts, electrosensitizers) [2, 3] and the development of materials with the extensive functional potentials on their basis [4,5].Along with the development of electrochemical procedures for the synthesis of photosensitive, organized molecular structures on the basis of the transition metal complexes, the studies of photochemical and photophysical activity of macrocyclic compounds and their ability to take part in photo-induced aggregation processes resulting in polynuclear structures are continued [6][7][8][9]. The most interesting for the development of photoactive polynuclear systems are the square-planar Pt(II) and Pd(II) complexes [10], including those with the Salen-type ligands.As was previously established, the Pt(II) complexesluminesce at T = 293 and 77 K and are characterized by the lowest-lying triplet electronically excited state (ees) with metal-to-ligand charge transfer ( MLCT ).It was found also [8,12] that complexes I , III , and IV in glassy matrices at T = 77 K and high monomer concentrations in solution can form luminescing associates, this process being most efficient for complex IV . In this case, at T = 293 K, in addition to the radiating and nonradiating deactivation of the ees energy, this complex also forms excimers. The results obtained showed that the changing donor-acceptor properties of the ligands in a series Salen-Salpn-1,2-Salpn-1,3 are responsible for essential changes in the properties of the corresponding Pt complexes, which are revealed in both electropolymerization and photophysical processes [9].We previously reported that the bimolecular photochemical reaction in the [Pt(Salen)] solutions gives only one product, i.e., a dimer, with luminescent properties [13]. We also assumed that a possible photochemical reaction resulting in the dimeric product can be the reaction of intermolecular photocyclization with participation of azomethine (-N=CH-) group of a ligand in particular, of a mobile hydrogen atom at the β -C atom (Fig. 1a). In this case, the ees of [Pt(Salen)] with MLCT brings about weakening and homolysis of the C-H bond in azomethine group and further formation of two covalent C-C bonds and dihydrogen. In a new supramolecule formed, the planes of both molecules can be arranged at an angle of 180° to one another (Fig. 1b). Moreover, a metal center can be partially oxidized to Pt(III), since the formation of ees of every monomer is attended by the electron density transfer from a metal center...
