一种新奇的d-f异双核配合物[Fe(phen)_3]_2[FeCe(tiron)_3]·6H_2O的水热合成、晶体结构和磁性

硝酸铁,硝酸铈,邻菲咯啉(phen)和钛铁试剂(Tiron)通过水热方法合成了一种d-f异双核配合物Fe(phen)3]2FeCe(tiron)3]·6H2O,tiron=C6H2O8S2。X-射线单晶衍射分析表明,晶体属立方晶系,P213空间群,晶胞参数为:a=2.19409(4)nm,V=10.5624(3)nm3,Z=4,F(000)=4648,R1=0.0451,wR2=0.1077,S=1.072。在具有C3对称性的FeCe(tiron)3]6-单元中,Fe髥与6个酚氧配位形成一个反三棱柱配位多面体,Ce髥则与3个桥联的酚氧μ2-O和3个磺酸基的氧形成另一个与FeO6共用底面的反三棱柱配位多面体CeO6。配阳离子通过phen-phen之间的π-π相互作用和与配阴离子间的静电引力等作用组装成一种三角梅状准主/客体型的超分子。在2~300K温度范围内测试了配合物的变温磁化率,结果表明,Ce髥-Fe髥之间存在典型的反铁磁性相互作用。

A Novel d-f Heterodinuclear Complex: Hydrothermal Synthesis,Crystal Structure and Magnetic Property of [Fe(phen)_3]_2[FeCe(tiron)_3]·6H_2O

A d-f heterodinuclear complexes Fe(phen)_3]_2FeCe(tiron)_3]·6H_2O (tiron=C_6H_2O_8S_2) was isolated from the hydrothermal reaction of Ce(NO_3)_3·6H_2O, Fe(NO_3)_3·9H_2O, 1,10-phenanthroline and 4,5-dihydroxybenzene-1,3-disul-fonate, and characterized by elemental analysis, IR, UV, TG and single-crystal X-ray diffraction analysis. The complex crystallized in the cubic system, space group P213 with the cell parameters: α=2.194 09(4) nm, V=10.562 4(3) nm~3, Z=4, F(000)=4 648, R_1=0.045 1, wR_2=0.107 7, S=1.07. In FeCe(tiron)_3]~(6-) unit with symmetry of C_3 was revealed that the Fe~(3+) ion is in a FeO_6 distorted trigonal anti-prism coordination polyhedron completed by six phenolate O atoms from three tiron~- ligands, and Ce~(3+) in a CeO_6 distorted trigonal anti-prism coordination polyhedron completed by three phenolateμ_2-O atoms and three O atoms from sulfonic group of three ligands. The Fe (phen)_3]~(3+) cations and FeCe(tiron)_3]~(6-) anions via or-or interaction between phen ligands and electric attraction between cations and anions was assembled into pseudo Host-guest type supramolecule in bougainvillea glabra-like. The magnetic properties of the complex has been determined in the temperature range 2～300 K, indicating that the antiferro-magnetic interaction between the central Ce(Ⅲ)-Fe(Ⅲ) ions.