Slyvka Y. Structural chemistry of Cu(I) and Ag(I) π-complexes with allyl derivatives of azoles

The thesis is devoted to the development of synthetic approaches, crystal structure investigation and exploration of main crystal engineering features of copper(I) and silver(I) π-complexes with allylic derivatives of azoles (triazole, tetrazole, thiadiazole, oxadiazole), as well as to the investigation of their non-linear optical properties. Using the alternating-current electrochemical technique as well as by the direct reactions 107 novel coordination compounds (among which 80 copper(I) π-complexes and 22 silver(I) π-coordination compounds with allyl derivatives of azoles) have been obtained and structurally studied. 31 Organic ligands, N-, O- and S-allyl (both mono- and diallyl) derivatives of azoles (1,2,3-triazole, 1,2,4-triazole, tetrazole, 1,3,4-oxadiazole and 1,3,4-thiadiazole) were designed and synthesized. All obtained 107 coordination compounds as well as 6 organic allylic ligands (based on 1,2,3-triazole, tetrazole and 1,3,4-thiadiazole) were studied using single crystal X-ray diffraction. A thorough crystal chemical analysis of the structures of copper(I) π-complexes based on allyl derivatives of azoles allowed us to identify 55 ways of coordination constructions (and nodes) organizations, covering the range from isolated fragments with terminal anions to the polymeric frameworks. Quantum chemical DFT calculations (geometry optimization, electron structure calculation, calculations of dipole moment, hyperpolarizability and theoretical Raman and UV-VIS spectra) allowed to explain the main features of the π-complexes structures and their properties. Nonlinear optical (NLO) investigation of obtained crystalline copper(I) π-complexes ravealed a hight efficiency laser stimulated second harmonic generation (SHG) and third harmonic generation (THG).