Barta Cheri A, Bayly Simon R, Read Paul W, Patrick Brian O, Thompson Robert C, Orvig Chris
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada.
Inorg Chem. 2008 Apr 7;47(7):2280-93. doi: 10.1021/ic701612e. Epub 2008 Mar 5.
A series of cationic, trimetallic d/f/d complexes have been prepared which use a multidentate, macrocyclic amine phenol ligand to coordinate divalent first row d-block transition metal ions (TM) and lanthanides (Ln) ions in close proximity, desirable for magnetic studies. Isolable complexes of the d/f/d cluster compounds with the formula [Ln(TM)2(bcn)2]ClO4.nH2O, where H3bcn is tris-N, N', N''-(2-hydroxybenzyl)-1,4,7-triazacyclononane, TM = Zn(II) and Ni(II) and Ln = La(III), Nd(III), Gd(III), Dy(III), and Yb(III), were synthesized by a one-pot sequential reaction of stoichiometric amounts of H 3bcn with the TM(II) and Ln(III) metal ions. The spontaneously formed cationic complexes were characterized by a variety of analytical techniques including IR, NMR, +ESI-MS, and EA. The [TM(Hbcn)].nH2O and [TM3(bcn)2].nH2O complexes were also synthesized to probe the building blocks of the d/f/d coaggregated species. The solid-state X-ray crystal structures of [GdNi2(bcn)2(CH3CN)2]ClO4.CH3CN and [GdZn2(bcn)2(CH3CN)2]ClO4.CH3CN were determined to be nearly identical with each TM(II) encapsulated in an octahedral geometry by the N3O3 binding pocket of the bcn (3-) ligand. The eight coordinate Gd(III) was bicapped by two TM(bcn) moieties and coordinated by two solvent molecules. Because of the isostructurality of the [LnZn2(bcn)2]ClO4.nH2O and [LnNi2(bcn)2]ClO4.nH2O complexes, an empirical approach using the LnZn2 magnetic data was utilized to remove first-order anisotropic contributions from the LnNi2 species. Ferromagnetic spin interactions were determined for the [LnNi2(bcn)2]ClO4.nH2O complexes, where Ln = Gd(III), Dy(III), and Yb(III), while an antiferromagnetic exchange was observed for Ln = Nd(III).
已制备出一系列阳离子三金属d/f/d配合物，它们使用多齿大环胺酚配体来配位二价第一排d区过渡金属离子（TM）和镧系元素（Ln）离子，且二者距离很近，这对磁性研究很有利。合成了通式为[Ln(TM)2(bcn)2]ClO4·nH2O的d/f/d簇合物的可分离配合物，其中H3bcn为三-N，N'，N''-(2-羟基苄基)-1,4,7-三氮杂环壬烷，TM = Zn(II)和Ni(II)，Ln = La(III)、Nd(III)、Gd(III)、Dy(III)和Yb(III)，通过化学计量的H3bcn与TM(II)和Ln(III)金属离子进行一锅法顺序反应来合成。通过包括红外光谱（IR）、核磁共振（NMR）、正电喷雾电离质谱（+ESI-MS）和元素分析（EA）等多种分析技术对自发形成的阳离子配合物进行了表征。还合成了[TM(Hbcn)]·nH2O和[TM3(bcn)2]·nH2O配合物以探究d/f/d共聚集物种的结构单元。测定了[GdNi2(bcn)2(CH3CN)2]ClO4·CH3CN和[GdZn2(bcn)2(CH3CN)2]ClO4·CH3CN的固态X射线晶体结构，发现每个TM(II)都被bcn(3-)配体的N3O3结合口袋以八面体几何构型包封，二者几乎相同。八配位的Gd(III)由两个TM(bcn)部分双帽封，并由两个溶剂分子配位。由于[LnZn2(bcn)2]ClO4·nH2O和[LnNi2(bcn)2]ClO4·nH2O配合物的同构性，利用一种基于LnZn2磁性数据的经验方法来消除LnNi2物种的一阶各向异性贡献。对于[LnNi2(bcn)2]ClO·nH2O配合物（其中Ln = Gd(III)、Dy(III)和Yb(III)）确定存在铁磁自旋相互作用，而对于Ln = Nd(III)则观察到反铁磁交换。
