| Autor: |
Tarakanov PA; Institute of Physiologically Active Compounds at Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, 1 Severny Proezd, 142432 Chernogolovka, Russian Federation. tarakanov_pa@ipac.ac.ru., Simakov AO; Institute of Physiologically Active Compounds at Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, 1 Severny Proezd, 142432 Chernogolovka, Russian Federation. tarakanov_pa@ipac.ac.ru., Pushkarev VE; Institute of Physiologically Active Compounds at Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, 1 Severny Proezd, 142432 Chernogolovka, Russian Federation. tarakanov_pa@ipac.ac.ru., Konev DV; Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, 1 Academician Semenov Avenue, 142432 Chernogolovka, Russian Federation., Goncharova OA; Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, 1 Academician Semenov Avenue, 142432 Chernogolovka, Russian Federation., Slesarenko NA; Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, 1 Academician Semenov Avenue, 142432 Chernogolovka, Russian Federation., Tarakanova EN; Institute of Physiologically Active Compounds at Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, 1 Severny Proezd, 142432 Chernogolovka, Russian Federation. tarakanov_pa@ipac.ac.ru.; Research Institute of Macroheterocycles, Ivanovo State University of Chemistry and Technology, RF-153000 Ivanovo, Russian Federation. tarakanova.ek.nik@gmail.com., Nefedov SE; Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, 119991 Moscow, Russian Federation., Stuzhin PA; Research Institute of Macroheterocycles, Ivanovo State University of Chemistry and Technology, RF-153000 Ivanovo, Russian Federation. tarakanova.ek.nik@gmail.com. |
| Abstrakt: |
A series of 5,7-disubstituted 1,4-diazepinoporphyrazinato magnesium(II) and nickel(II) complexes, including two novel compounds, were obtained by metal-templated macrocyclization. A combination of X-ray diffraction, 1 H NMR, UV-vis, and electrochemical analyses allowed us to study their tendency towards H-type dimerization and trace the influence of structural and solvation factors on dimer stability. Based on the physicochemical and theoretical DFT calculation data, it was found that the main binding forces between 6 H -1,4-diazepinoporphyrazine decks in the dimers were efficient π-π donor-acceptor interactions induced by the interdeck C-H⋯N hydrogen bonds. Furthermore, the metal-ligand (Pz 2- → M 2+ ) electronic interactions have a key influence on the π-π stacking of the porphyrazine cores. It was shown that the displacement of the metal ion out of the macrocycle plane induced by coordinating agents can trigger the dissociation of the dimer, since the resulting enhancement of the donor-acceptor electronic interaction between the metal ion and the π-system of the ligand leads to a subsequent weakening of the π-π stacking of the porphyrazine cores. The TD-DFT calculations predicted the non-degeneracy of the HOMO-1 → LUMO and HOMO → LUMO+1 transitions in the 6 H -1,4-diazepinoporphyrazine H -dimers, which explains the Q-band splitting in their UV-vis spectra. |
