| Autor: |
Tarakanova EN; Research Institute of Macroheterocycles, Ivanovo State University of Chemistry and Technology, RF-153000 Ivanovo, Russia. tarakanova.ek.nik@gmail.com and Institute of Physiologically Active Compounds, Russian Academy of Sciences, 1 Severny Proezd, Chernogolovka 142432, Moscow Region, Russian Federation. pushkarev@ipac.ac.ru., Tarakanov PA; Institute of Physiologically Active Compounds, Russian Academy of Sciences, 1 Severny Proezd, Chernogolovka 142432, Moscow Region, Russian Federation. pushkarev@ipac.ac.ru and Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 Academician Semenov Avenue, Chernogolovka 142432, Moscow Region, Russian Federation., Simakov AO; Institute of Physiologically Active Compounds, Russian Academy of Sciences, 1 Severny Proezd, Chernogolovka 142432, Moscow Region, Russian Federation. pushkarev@ipac.ac.ru., Furuyama T; Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan., Kobayashi N; Faculty of Textile Science and Technology, Shinshu University, Tokida, Ueda 386-8567, Japan., Konev DV; Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 Academician Semenov Avenue, Chernogolovka 142432, Moscow Region, Russian Federation and D. I. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya sq., 125047, Moscow, Russian Federation., Goncharova OA; Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 Academician Semenov Avenue, Chernogolovka 142432, Moscow Region, Russian Federation., Trashin SA; Institute of Physiologically Active Compounds, Russian Academy of Sciences, 1 Severny Proezd, Chernogolovka 142432, Moscow Region, Russian Federation. pushkarev@ipac.ac.ru and AXES Research Group, Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerpen, Belgium., De Wael K; AXES Research Group, Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerpen, Belgium., Sulimenkov IV; Chernogolovka Branch of the N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 1/10 Academician Semenov Avenue, Chernogolovka 142432, Moscow Region, Russian Federation., Filatov VV; Chernogolovka Branch of the N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 1/10 Academician Semenov Avenue, Chernogolovka 142432, Moscow Region, Russian Federation., Kozlovskiy VI; Chernogolovka Branch of the N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 1/10 Academician Semenov Avenue, Chernogolovka 142432, Moscow Region, Russian Federation., Tomilova LG; Institute of Physiologically Active Compounds, Russian Academy of Sciences, 1 Severny Proezd, Chernogolovka 142432, Moscow Region, Russian Federation. pushkarev@ipac.ac.ru and Department of Chemistry, M.V. Lomonosov Moscow State University, 1 Leninskie Gory, 119991 Moscow, Russian Federation., Stuzhin PA; Research Institute of Macroheterocycles, Ivanovo State University of Chemistry and Technology, RF-153000 Ivanovo, Russia. tarakanova.ek.nik@gmail.com., Pushkarev VE; Institute of Physiologically Active Compounds, Russian Academy of Sciences, 1 Severny Proezd, Chernogolovka 142432, Moscow Region, Russian Federation. pushkarev@ipac.ac.ru. |
| Abstrakt: |
Reaction of (2,3,9,10,16,17,23,24-octabutylphthalocyaninato)lanthanide(iii) acetylacetonates (BuPcLn(acac), 1a-c, Ln = Lu (a), Eu (b), La (c)) with a tetrakis(5,7-bis(4-tert-butylphenyl)-6H-1,4-diazepino)[2,3-b,g,l,q]porphyrazine ligand (tBuPhDzPzH2, 2) produced sandwich compounds (tBuPhDzPz)Ln(BuPc) (3a-c), which represent the first heteroleptic double-deckers incorporating both Pc and DzPz decks. A combination of high-resolution mass spectrometry, UV-Vis/NIR, MCD, and 1H NMR spectroscopy, and square-wave voltammetry provided unambiguous characterization of target complexes 3 indicating that their spectral and electrochemical properties are generally intermediate with respect to their homoleptic relatives. Based on the data of solution-state 1H-1H NMR (COSY, NOESY) correlation spectroscopy supported by DFT calculations, a dimerization tendency of compounds 3 proportional to the Ln(iii) ion size was found. The spectroelectrochemical study of 3 and the corresponding homoleptic double-deckers revealed a pronounced tendency to aggregation of the one-electron oxidized forms of DzPz-containing double-decker complexes compared to homoleptic Pc2Ln compounds. |
