title: Symmetry-based magnetic anisotropy in the trigonal bipyramidal cluster [Tp2(Me3tacn)3Cu3Fe2(CN)6]4+.
abstract: Reaction of [(Me3tacn)Cu(H2O)2]2+ (Me3tacn = N,N',N' '-trimethyl-1,4,7-triazacyclononane) with [TpFe(CN)3]- (Tp- = hydrotris(pyrazolyl)borate) in a mixture of ethanol and acetonitrile affords the pentanuclear cluster [Tp2(Me3tacn)3Cu3Fe2(CN)6]4+. Single-crystal X-ray analysis reveals a trigonal bipyramidal structure featuring a D3h-symmetry core in which two opposing FeIII (S = 1/2) centers are linked through cyanide bridges to an equatorial triangle of three CuII (S = 1/2) centers. Fits to variable-temperature dc magnetic susceptibility data are consistent with ferromagnetic coupling to give an S = 5/2 ground state, while fits to low-temperature magnetization data indicate the presence of a large axial zero-field splitting (D = -5.7 cm-1). Frequency dependence observed in the ac magnetic susceptibility data confirms single-molecule magnet behavior, with an effective spin reversal barrier of Ueff = 16 cm-1. When compared with the much lower anisotropy barrier previously observed for the face-centered cubic cluster [Tp8(H2O)6Cu6Fe8(CN)6]4+, the results demonstrate the enormous influence of the geometry in which a given set of metal ions are arranged.
authors.affiliation: Coordination Chemistry Institute and State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, China.
authors.forename: Cai-Feng
authors.initials: CF
authors.lastname: Wang
authors.forename: Jing-Lin
authors.initials: JL
authors.lastname: Zuo
authors.forename: Bart M
authors.initials: BM
authors.lastname: Bartlett
authors.forename: You
authors.initials: Y
authors.lastname: Song
authors.forename: Jeffrey R
authors.initials: JR
authors.lastname: Long
authors.forename: Xiao-Zeng
authors.initials: XZ
authors.lastname: You