Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)2]2+ building block: syntheses, crystal structures, and magnetic properties.
Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)2]2+ building block: syntheses, crystal structures, and magnetic properties.
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DOI：
10.1021/ic050181b
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发表时间：
2005-06
影响因子：
4.6
通讯作者：
Zhonghai Ni;H. Kou;Lei Zheng;Yi-hua Zhao;Lifang Zhang;Ruji J. Wang;A. Cui;O. Sato
中科院分区：
文献类型：
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作者：
Zhonghai Ni;H. Kou;Lei Zheng;Yi-hua Zhao;Lifang Zhang;Ruji J. Wang;A. Cui;O. Sato
两个新的氰基桥联异双核配合物[Mn（II）（phen）2Cl][Fe（III）（bpb）（CN）2] x0.5CH3CH2OHx1.5H2O（1）和[Mn（II）（phen）2Cl][Cr（III）（bpb）（CN）2] x2 H2O（2）[phen = 1，10-菲咯啉; bpb（2-）= 1，2-双（吡啶-2-甲酰胺基）苯酸盐]和四种新的叠氮基桥联的Mn（II）二聚络合物[Mn 2（phen）4（mu（1，合成了[Mn（III）（bpb）（CN）2] 2xH 2 O [M = Fe（3），Cr（4），Co（5）]和[Mn 2（phen）4（mu（1，3）-N3）（N3）2] BPh4x0.5H2O（6）配合物，并对其进行了单晶X射线衍射分析和磁性研究。配合物1和2由[Mn（phen）2Cl]+和[M（bpb）（CN）2]-单元通过一个[M（bpb）（CN）2]-氰基配体连接而成。配合物3-5是双端（EO）叠氮桥联的Mn（II）双核配合物，其中两个[M（bpb）（CN）2]-分子作为电荷补偿阴离子。然而，在配合物6中的Mn（II）离子通过单个端到端（EE）叠氮桥连配体与一个大的游离BPh 4（-）基团作为电荷平衡阴离子连接。根据哈密顿量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）之间的磁耦合为反铁磁性，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（Mn 1）S（Mn 2））。结果表明，该化合物具有反铁磁相互作用，J = -2.29（4）cm（-1）（H = -JS（Mn 1）S（Mn 2））.研究了EO叠氮桥联Mn（II）二聚体的磁结构相关性。
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.