title: Double-decker bis(tetradiazepinoporphyrazinato) rare earth complexes: crucial role of intramolecular hydrogen bonding.
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 [(tBuPh)DzPz]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-H(ax)N(meso) hydrogen bonding and O-HN(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.
authors.affiliation: Institute of Physiologically Active Compounds, Russian Academy of Sciences, 1 Severny proezd, 142432 Chernogolovka, Moscow Region, Russian Federation. tarakanova.ek.nik@gmail.com.
authors.forename: Ekaterina N
authors.initials: EN
authors.lastname: Tarakanova
authors.affiliation: Institute of Physiologically Active Compounds, Russian Academy of Sciences, 1 Severny proezd, 142432 Chernogolovka, Moscow Region, Russian Federation. tarakanova.ek.nik@gmail.com.
authors.forename: Stanislav A
authors.initials: SA
authors.lastname: Trashin
authors.affiliation: Centre for Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Oslo, P. O. Box 1033 Blindern, N-0315 Oslo, Norway.
authors.forename: Anton O
authors.initials: AO
authors.lastname: Simakov
authors.affiliation: Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
authors.forename: Taniyuki
authors.initials: T
authors.lastname: Furuyama
authors.affiliation: Department of Chemistry, M.V. Lomonosov Moscow State University, 1 Leninskie Gory, 119991 Moscow, Russian Federation. tom@org.chem.msu.ru.
authors.forename: Alexander V
authors.initials: AV
authors.lastname: Dzuban
authors.affiliation: Institute for Problems of Chemical Physics, Russian Academy of Sciences, 1 Semenov Prospect, 142432 Chernogolovka, Moscow region, Russian Federation.
authors.forename: Liana N
authors.initials: LN
authors.lastname: Inasaridze
authors.affiliation: Institute of Physiologically Active Compounds, Russian Academy of Sciences, 1 Severny proezd, 142432 Chernogolovka, Moscow Region, Russian Federation. tarakanova.ek.nik@gmail.com.
authors.forename: Pavel A
authors.initials: PA
authors.lastname: Tarakanov
authors.affiliation: Institute for Problems of Chemical Physics, Russian Academy of Sciences, 1 Semenov Prospect, 142432 Chernogolovka, Moscow region, Russian Federation and Skolkovo Institute of Science and Technology, Nobel St. 3, 143026 Moscow, Russian Federation.
authors.forename: Pavel A
authors.initials: PA
authors.lastname: Troshin
authors.affiliation: Institute of Physiologically Active Compounds, Russian Academy of Sciences, 1 Severny proezd, 142432 Chernogolovka, Moscow Region, Russian Federation. tarakanova.ek.nik@gmail.com.
authors.forename: Victor E
authors.initials: VE
authors.lastname: Pushkarev
authors.affiliation: Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
authors.forename: Nagao
authors.initials: N
authors.lastname: Kobayashi
authors.affiliation: Institute of Physiologically Active Compounds, Russian Academy of Sciences, 1 Severny proezd, 142432 Chernogolovka, Moscow Region, Russian Federation. tarakanova.ek.nik@gmail.com and Department of Chemistry, M.V. Lomonosov Moscow State University, 1 Leninskie Gory, 119991 Moscow, Russian Federation. tom@org.chem.msu.ru.
authors.forename: Larisa G
authors.initials: LG
authors.lastname: Tomilova