Double-decker bis(tetradiazepinoporphyrazinato) rare earth complexes: Crucial role of intramolecular hydrogen bonding

Ekaterina N. Tarakanova, Stanislav A. Trashin, Anton O. Simakov, Taniyuki Furuyama, Alexander V. Dzuban, Liana N. Inasaridze, Pavel A. Tarakanov, Pavel A. Troshin, Victor E. Pushkarev, Nagao Kobayashi, Larisa G. Tomilova

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

A series of homoleptic bis{tetrakis(5,7-bis(4-tert-butylphenyl)-6H-1,4-diazepino)[2,3-b,g,l,q]porphyrazinato}lanthanide sandwich complexes [tBuPhDzPz]2Ln (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-Hax⋯Nmeso hydrogen bonding and O-H⋯NDz 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.

Original languageEnglish
Pages (from-to)12041-12052
Number of pages12
JournalDalton Transactions
Volume45
Issue number30
DOIs
Publication statusPublished - 2016

ASJC Scopus subject areas

  • Inorganic Chemistry

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