Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)2]2+ building block: Syntheses, crystal structures, and magnetic properties

Zhong Hai Ni, Hui Zhong Kou, Lei Zheng, Yi Hua Zhao, Li Fang Zhang, Ru Ji Wang, Ai Li Cui, Osamu Sato

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Abstract

Two new cyano-bridged heterobinuclear complexes, [MnII(phen) 2Cl][FeIIIl(bpb)(CN)2]·0.5CH 3CH2OH·1.5H2O (1) and [Mn II(phen)2Cl][CrIII(bpb)(CN)2] ·2H2O (2) [phen = 1,10-phenanthroline; bpb2 = 1,2-bis(pyridine-2-carboxamido)-benzenate], and four novel azido-bridged Mn(II) dimeric complexes, [Mn2(phen)41,1-N 3)2][MIII(bpb)(CN)2] 2·H2O [M = Fe (3), Cr (4), Co (5)] and [Mn 2(phen)41,3-N3)(N 3)2]BPh4·0.5H2O (6), have been synthesized and characterized by single-crystal X-ray diffraction analysis and magnetic studies. Complexes 1 and 2 comprise [Mn(phen)2Cl] + and [M(bpb)(CN)2]- units connected by one cyano ligand of [M(bpb)(CN)2]-. Complexes 3-5 are doubly end-on (EO) azido-bridged Mn(II) binuclear complexes with two [M(bpb)(CN) 2]- molecules acting as charge-compensating anions. However, the Mn(II) ions in complex 6 are linked by a single end-to-end (EE) azido bridging ligand with one large free BPh4- group as the charge-balancing anion. The magnetic coupling between Mn(II) and Fe(III) or Cr(III) in complexes 1 and 2 was found to be antiferromagnetic with J MnFe = -2.68(3) cm-1 and JMnCr = -4.55(1) cm-1 on the basis of the Hamiltonian Ĥ = - JŜMnŜM(M = Fe or Cr). The magnetic interactions between two Mn(II) ions in 3-5 are ferromagnetic in nature with the magnetic coupling constants of 1.15(3), 1.05(2), and 1.27(2) cm-1 (Ĥ = -JŜMn1ŜMn2), respectively. The single EE azido-bridged dimeric complex 6 manifests antiferromagnetic interaction with J = -2.29(4) cm-1 (Ĥ = - JŜMn1ŜMn2). Magneto-structural correlationship on the EO azido-bridged Mn(II) dimers has been investigated.

Original languageEnglish
Pages (from-to)4728-4736
Number of pages9
JournalInorganic chemistry
Volume44
Issue number13
DOIs
Publication statusPublished - Jun 27 2005
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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