含庞大[Mn(phen)₂]²⁺结构单元的叠氮基或氰基桥联双核配合物的组装：合成、晶体结构及磁性质

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

作者信息

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

机构信息

Department of Chemistry, Tsinghua University, Beijing 100084, PR China.

出版信息

Inorg Chem. 2005 Jun 27;44(13):4728-36. doi: 10.1021/ic050181b.

DOI:10.1021/ic050181b

PMID:15962981

Abstract

Two new cyano-bridged heterobinuclear complexes, [Mn(II)(phen)2Cl][Fe(III)(bpb)(CN)2] x 0.5CH3CH2OH x 1.5H2O (1) and [Mn(II)(phen)2Cl][Cr(III)(bpb)(CN)2] x 2H2O (2) [phen = 1,10-phenanthroline; bpb(2-) = 1,2-bis(pyridine-2-carboxamido)benzenate], and four novel azido-bridged Mn(II) dimeric complexes, [Mn2(phen)4(mu(1,1)-N3)2][M(III)(bpb)(CN)2]2 x H2O [M = Fe (3), Cr (4), Co (5)] and [Mn2(phen)4(mu(1,3)-N3)(N3)2]BPh4 x 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 J(MnCr) = -4.55(1) cm(-1) on the basis of the Hamiltonian H = -JS(Mn)S(M) (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) (H = -JS(Mn1)S(Mn2)), respectively. The single EE azido-bridged dimeric complex 6 manifests antiferromagnetic interaction with J = -2.29(4) cm(-1) (H = -JS(Mn1)S(Mn2)). Magneto-structural correlationship on the EO azido-bridged Mn(II) dimers has been investigated.

摘要

合成了两种新型氰基桥联异双核配合物，[Mn(II)(phen)2Cl][Fe(III)(bpb)(CN)2]·0.5CH3CH2OH·1.5H2O (1) 和 [Mn(II)(phen)2Cl][Cr(III)(bpb)(CN)2]·2H2O (2) [phen = 1,10 - 菲咯啉；bpb(2 - ) = 1,2 - 双(吡啶 - 2 - 甲酰胺基)苯甲酸盐]，以及四种新型叠氮基桥联的Mn(II)二聚体配合物，[Mn2(phen)4(μ(1,1)-N3)2][M(III)(bpb)(CN)2]2·H2O [M = Fe (3), Cr (4), Co (5)] 和 [Mn2(phen)4(μ(1,3)-N3)(N3)2]BPh4·0.5H2O (6)，并通过单晶X射线衍射分析和磁性研究对其进行了表征。配合物1和2由[Mn(phen)2Cl]+和[M(bpb)(CN)2]-单元组成，通过[M(bpb)(CN)2]-的一个氰基配体相连。配合物3 - 5是双端基（EO）叠氮基桥联的Mn(II)双核配合物，两个[M(bpb)(CN)2]-分子作为电荷补偿阴离子。然而，配合物6中的Mn(II)离子通过单个端对端（EE）叠氮基桥联配体相连，有一个大的游离BPh4(-)基团作为电荷平衡阴离子。基于哈密顿量H = -JS(Mn)S(M)（M = Fe或Cr），发现配合物1和2中Mn(II)与Fe(III)或Cr(III)之间的磁耦合是反铁磁性的，J(MnFe) = -2.68(3) cm(-1)，J(MnCr) = -4.55(1) cm(-1)。3 - 5中两个Mn(II)离子之间的磁相互作用本质上是铁磁性的，磁耦合常数分别为1.15(3)、1.05(2)和1.27(2) cm(-1)（H = -JS(Mn1)S(Mn2)）。单EE叠氮基桥联的二聚体配合物6表现出反铁磁性相互作用，J = -2.29(4) cm(-1)（H = -JS(Mn1)S(Mn2)）。研究了EO叠氮基桥联的Mn(II)二聚体的磁结构相关性。