Double-decker bis(tetradiazepinoporphyrazinato) rare earth complexes: crucial role of intramolecular hydrogen bonding. Issue 30 (11th July 2016)

• Record Type: Journal Article
• Authors: Tarakanova, Ekaterina N.; Trashin, Stanislav A.; Simakov, Anton O.; Furuyama, Taniyuki; Dzuban, Alexander V.; Inasaridze, Liana N.; Tarakanov, Pavel A.; Troshin, Pavel A.; Pushkarev, Victor E.; Kobayashi, Nagao; Tomilova, Larisa G.
• Is Part Of: Dalton transactions. Volume 45:Issue 30(2016)
• Page Start: 12041
• Page End: 12052
• Publication Date: 2016-07-11
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c6dt01779g
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Study focuses on specific interactions in diazepine-containing macroheterocycles. Abstract : A series of homoleptic bis{tetrakis(5, 7-bis(4- tert -butylphenyl)-6 H -1, 4-diazepino)[2, 3- b, g, l, q ]porphyrazinato}lanthanide sandwich complexes [ t BuPh DzPz]2 Ln (Ln = Lu, Er, Dy, Eu, Nd, Ce, La) were prepared and their physicochemical properties were studied to gain insight into the nature of specific interactions in diazepinoporphyrazines. The effect of annulated diazepine moieties and the Ln ionic radius on the properties of the complexes was investigated in comparison with double-decker phthalocyanines. A combination of experimental and theoretical studies revealed the presence of two types of hydrogen bonding interactions in the metal-free porphyrazine and the corresponding sandwich complexes, namely, interligand C–H ax ⋯N meso hydrogen bonding and O–H⋯N Dz ligand–water interaction. The interligand hydrogen bonding imparts high stability of the ligand dimer and the double-decker compounds in a reduced state. This work is the first comprehensive investigation into the fundamental understanding of the unusual properties of diazepine-containing macroheterocycles.