Pressure-stabilized low-spin state for binuclear iron(III) spin-crossover compounds

Shinya Hayami, Yuko Hosokoshi, Katsuya Inoue, Yasuaki Einaga, Osamu Sato, Yonezo Maeda

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Abstract

Binuclear iron(III) spin-crossover complexes with salten ligand [Fe 2(salten) 2(L)](BPh 4) 2 were synthesized and characterized by single-crystal X-ray diffraction, M6ssbauer spectra, magnetic susceptibilities and electronic spectra, where H 2salten is a pentadentate ligand derived from salicylaldehyde and 3,3′-diaminodipropylamine and L is a didentate axial ligand (az = azobis(4-pyridine) and cc = 4,4′-vinylenebis(pyridine)). The structures of [Fe 2(salten) 2(az)](BPh 4) 2 (1) and [Fe 2(salten) 2(cc)](BPh 4) 2 (2) were determined at both 100 K and 298 K. Crystal data for 1 at 100 K: C 98H 94 O 4N 10B 2Fe 2, monoclinic, space group P2 1/c, Z = 2, a = 15.986(2) Å, b = 15.825(2) Å, c = 16.441(2) Å, β = 107.902(2)°, V = 3957.8(8) Å 3. Crystal data for 2 at 100 K: C 100H 96 O 4N 8B 2Fe 2, monoclinic, space group P2 1/a, Z = 2, a = 16.4296(8) Å, b = 15.747(1) Å, c = 16.637(1) Å, β = 109.2375(9)° and Z = 2. The complexes 1 and 2 exhibited the spin-crossover behavior depending on temperature within the temperature range of 200 to 350 K, and rapid spin equilibrium behavior was observed by means of M6ssbauer spectroscopy at 293 K. The complexes 1 and 2 also exhibited a pressure-induced spin transition between the rapid spin equilibrium state and low-spin state at 300 K. Such a pressure-induced spin transition has not been reported earlier.

Original languageEnglish
Pages (from-to)2361-2368
Number of pages8
JournalBulletin of the Chemical Society of Japan
Volume74
Issue number12
DOIs
Publication statusPublished - 2001 Dec 1

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ASJC Scopus subject areas

  • Chemistry(all)

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