Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Cyanide-Bridged CrIIIMnII Binuclear Complexes Based on [Mn(phen)2]2+ and Dicyanidechromate(III) Building Blocks: Syntheses, Crystal Structures, and Magnetic Properties

  • Li, Guo-Ling (School of Chemical Engineering and Technology, China University of Mining and Technology) ;
  • Zhang, Li-Fang (School of Chemical Engineering and Technology, China University of Mining and Technology) ;
  • Ni, Zhong-Hai (School of Chemical Engineering and Technology, China University of Mining and Technology) ;
  • Kou, Hui-Zhong (Department of Chemistry, Tsinghua University) ;
  • Cui, Ai-Li (Department of Chemistry, Tsinghua University)
  • Received : 2012.02.06
  • Accepted : 2012.02.17
  • Published : 2012.05.20
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Abstract

Three new cyanide-bridged $Cr^{III}Mn^{II}$ binuclear complexes, $[Mn(phen)_2Cl][Cr(bpmb)(CN)_2]{\cdot}H_2O$ ($\mathbf{1}$) (phen = 1,10-phenanthroline, $bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate), $[Mn(phen)_2Cl][Cr(bpmb)-(CN)_2]{\cdot}H_2O$ ($\mathbf{2}$) ($bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate), and $[Mn(phen)_2Cl]-[Cr(bpClb)(CN)_2]{\cdot}CH_3OH{\cdot}H_2O$ ($\mathbf{3}$) ($bpClb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate) were obtained based on $Mn(phen)_2Cl_2$ and a series of dicyanidechromate(III) building blocks. Single crystal X-ray diffraction analysis shows the structures of the three complexes are dimeric type with two different metal centers linked by a cyanide group from corresponding dicyanidechromate(III) building block. Magnetic investigations indicate the existence of relatively weak antiferromagnetic coupling between Cr(III) and Mn(II) ions with best-fit constants $J_{CrMn}=-2.78(5)cm^{-1}$ for $\mathbf{1}$, $J_{CrMn}=-3.02(2)cm^{-1}$ for $\mathbf{2}$ and $J_{CrMn}=-2.27(3)cm^{-1}$ for $\mathbf{3}$ based on the spin exchange Hamiltonian = $-2J_{CrMn}\hat{S}_{Cr}\hat{S}_{Mn}$. The magneto-structural correlation of cyanide-bridged $Cr^{III}Mn^{II}$ complexes has been discussed at last.

Keywords

References

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