Synthesis and magnetic properties of iron(III) complexes bridged by 1,1′-tetramethylenediimidazole exhibiting an infinite zigzag-chain structure

Mika Fukuya, Masaaki Ohba, Ken Ichiro Motoda, Naohide Matsumoto, Hisashi Okawa, Yonezo Maeda

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Abstract

Three polymeric iron(III) complexes [Fe(tdim)Ln]ClO4 (L = L1 1, L2 or L3 3) consisting of a bridging ligand (tdim = 1,1′-tetramethylenediimidazole) and a quadridentate Schiff base ligand have been prepared and characterized, where H2Ln = RN(CH2)2NR′ [R = R′ = MeC(OH)=CHCMe=, n = 1; R = R′ = o-HOC6H4CH=, n = 3; R = MeC(OH)=CHCMe=, R′ = o-HOC6H4CH=, n = 2]. Magnetic susceptibility data (4.2-300 K) showed that 1 is low spin (S = 1/2), 2 of spin equilibrium (S = 5/2 ⇌ 1/2), and 3 essentially high spin (S = 5/2) and exhibiting an unusual behaviour below ca. 100 K. The spin equilibrium of 2 occurs over a wider temperature range than that of the corresponding mononuclear complex [Fe(mim)2L2]ClO4 (mim = 1-methylimidazole). A crystal structure analysis of 3 confirmed that it has an infinite zigzag-chain structure and the iron(III) ion is six-co-ordinated by N2O2 donor atoms of the quadridentate ligand, an imidazole nitrogen atom of a bridging ligand and a nitrogen atom of the adjacent bridging ligand. The crystal structure also shows that 3 suffers from disorder and there are two configurations A and B with respect to the orientation of the imidazole moiety, having populations of 0.65 and 0.35, respectively. The unusual magnetic behaviour is rationalized by the crystal structure, Mössbauer and ESR spectra.

Original languageEnglish
Pages (from-to)3277-3281
Number of pages5
JournalJournal of the Chemical Society, Dalton Transactions
Issue number22
DOIs
Publication statusPublished - Dec 1 1993

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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