【2022年1月締切】CiNii ArticlesへのCiNii Researchへの統合に伴う機関認証の移行確認について

【1/6更新】2022年4月1日からのCiNii ArticlesのCiNii Researchへの統合について

Synthesis and Structural Characterization of Dinuclear Manganese(III) Complexes with Cyclam-Based Macrocyclic Ligands Having Schiff-Base Pendant Arms as Chelating Agents

  • Wada Shusaku
    Department of Chemistry and Open Research Center for Coordination Molecule-based Devices, School of Science and Technology, Kwansei Gakuin University
  • Mikuriya Masahiro
    Department of Chemistry and Open Research Center for Coordination Molecule-based Devices, School of Science and Technology, Kwansei Gakuin University

抄録

Reaction of a series of dodecadentate ligands (H4L), 1,4,8,11-tetrakis(salicylideneaminoethyl)-1,4,8,11-tetraazacyclotetradecane and its substituted derivatives, with manganese(II) salts afforded ten dinuclear manganese(III) complexes, [Mn2X2L] (X = O2CCH3, O2CC6H5, and N3), which were characterized by analyzing infrared and electronic spectra and determining the temperature dependence of magnetic susceptibilities (4.5–300 K). Single-crystal X-ray crystallography of [Mn2(O2CCH3)2(tbsaec)]·2CHCl3 (3·2CHCl3) (H4tbsaec = 1,4,8,11-tetrakis(5-bromosalicylideneaminoethyl)-1,4,8,11-tetraazacyclotetradecane), [Mn2(O2CC6H5)2(tbsaec)] (4), [Mn2(O2CC6H5)2(tcsaec)] (6) (H4tcsaec = 1,4,8,11-tetrakis(5-chlorosalicylideneaminoethyl)-1,4,8,11-tetraazacyclotetradecane), [Mn2(N3)2(tnaec)]·2CHCl3 (7·2CHCl3) (H4tnaec = 1,4,8,11-tetrakis(2-hydroxy-1-naphthylmethylideneaminoethyl)-1,4,8,11-tetraazacyclotetradecane), [Mn2(O2CCH3)2(tmsaec)] (8) (H4tmsaec = 1,4,8,11-tetrakis(3-methoxysalicylideneaminoethyl)-1,4,8,11-tetraazacyclotetradecane) showed that each manganese(III) ion is chelated by two Schiff-base pendant arms outside the central tetraazacyclotetradecane ring, forming an axially compressed octahedron (for 3, 4, 6, and 8) or trigonal bipyramid (for 7) with an intramolecular Mn–Mn distance of 9.676(4)–10.096(2) Å. In accordance with the crystal structures, the magnetic interaction between the two manganese ions was very weak with a rather significant zero-field splitting of the manganese(III) ions.

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