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First MnIII complexes with tetradentate (N2O2) Schiff bases and tricyanomethanide: synthesis,crystal structure,and magnetic properties
Authors:V. A. Kopotkov  S. V. Simonov  O. V. Koplak  A. I. Dmitriev  E. B. Yagubskii
Affiliation:1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 prosp. Akad. Semenova, 142432, Chernogolovka, Moscow Region, Russian Federation
2. Institute of Solid State Physics, Russian Academy of Sciences, 2 ul. Akad. Osip’yana, 142432, Chernogolovka, Moscow Region, Russian Federation
Abstract:The first MnIII complexes with Schiff bases and tricyanomethanide-anion were synthesized: [Mn(salen)C(CN)3(H2O)] (1), [Mn(5-Brsalen)C(CN)3(H2O)] (2), [Mn(salpn)C(CN)3(H2O)] (3), [Mn(3-MeOsalen)C(CN)3(H2O)] (4), [Mn(5-Brsalen)(MeOH)(H2O)][C(CN)3] (5), and [Mn(3-MeOsalpn)(H2O)2][C(CN)3] (6), where SalenH2 is N,N′-bis(salicylidene)ethylenediamine, 5-BrsalenH2 is N,N′-bis(5-bromosalicylidene)ethylenediamine, SalpnH2 is N,N′-bis-(salicylidene)-1,3-diaminopropane, 3-MeOsalenH2 is N,N′-bis(3-methoxysalicylidene)-ethylenediamine, 3-MeOsalpnH2N,N′-bis(3-methoxysalicylidene)-1,3-diaminopropane. The tricyanomethanide anion in complexes 14 acts as a the terminal ligand, whereas in complexes 5 and 6 tricyanomethanide is not coordinated by MnIII and acts as an out-of-sphere counterion. The structures of complexes 14 are characterized by the formation of dimers due to hydrogen bonds between the water molecules and oxygen atoms of the Schiff bases. The Mn...Mn distances inside the dimers are 4.69–5.41 Å. Complex 6 has a zigzag chain structure consisting of the [Mn(3-MeOsalpn)(H2O)2]+ cations bound by double bridging aqua ligands. The study of the magnetic properties of complexes 1, 3, 4, and 6 showed the existence of antiferromagnetic interactions between the MnIII ions through the system of hydrogen bonds.
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