Synthesis and characterization of heteroleptic rare earth double-decker complexes involving tetradiazepinoporphyrazine and phthalocyanine macrocycles. Issue 18 (20th April 2021)

• Record Type: Journal Article
• Authors: Tarakanova, Ekaterina N.; Tarakanov, Pavel A.; Simakov, Anton O.; Furuyama, Taniyuki; Kobayashi, Nagao; Konev, Dmitry V.; Goncharova, Olga A.; Trashin, Stanislav A.; De Wael, Karolien; Sulimenkov, Ilya V.; Filatov, Vasily V.; Kozlovskiy, Viatcheslav I.; Tomilova, Larisa G.; Stuzhin, Pavel A.; Pushkarev, Victor E.
• Is Part Of: Dalton transactions. Volume 50:Issue 18(2021)
• Page Start: 6245
• Page End: 6255
• Publication Date: 2021-04-20
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d1dt00088h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : We report novel heteroleptic lanthanide sandwich complexes (Ln = Lu, Eu, La) and their spectral, electrochemical and computational studies. Abstract : Reaction of (2, 3, 9, 10, 16, 17, 23, 24-octabutylphthalocyaninato)lanthanide(iii ) acetylacetonates ( Bu PcLn(acac), 1a–c, Ln = Lu (a ), Eu (b ), La (c )) with a tetrakis(5, 7-bis(4- tert -butylphenyl)-6 H -1, 4-diazepino)[2, 3- b, g, l, q ]porphyrazine ligand ( t BuPh DzPzH2, 2 ) produced sandwich compounds ( t BuPh DzPz)Ln( Bu Pc) (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 1 H 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 1 H– 1 H 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 Pc2 Ln compounds.