两个锰的18-氮杂金属冠醚-6配合物的合成、晶体结构和磁性质研究

摘要

以负三价、五啮的Ⅳ-乙酰水杨酰肼(ashz3-)作为配体,合成了二个大环六核氮杂金属冠醚[MnⅢ6(ashz)6(MeOH)6]@6Me0H(1)和[MnⅢ6(ashz)6(DMF)6]@3DMF(2).晶体学数据是:配合物1,三方晶系,空间群R3,a=b=24.806(2),c=11.260(1)A,Z=3,μ=1.007mm-1,R=0.0572,wR=0.1142;配合物2,三方晶系,空间群R 3,a=b=26.629(3),c=23.298(4)A,Z=6,μ=0.856mm-1,R=0.0671,wR=0.1661.这两个配合物属18-氮杂金属冠醚-6结构类型,冠醚分子具有晶体学C3i对称性.配体ashz3-通过它的肼基的N-N桥连金属原子,从而形成有中央空穴的六核锰的大环配合物.变温磁化率(4～275K)研究表明,配合物1中金属离子间存在着反铁磁性耦合.%Two macrocyclic hexanuclear azaMetallacrowns, [MnⅢ6(ashz)6(MeOH)6] @ 6MeOH (1) and [MnⅢ6(ashz)6(DMF)6] @ 3DMF (2), were prepared using a trianionic pentadentate ligand N-acylsalicylhydrazide (ashz3-). The crystal data are trigonal R3, a = b = 24. 806 (2), c = 11. 260 ( 1 )A, Z = 3, μ = 1. 007mm- 1, R = 0. 0572, w R =0.1142 for complex 1 and trigonal R3, a=b=26.629(3), c=23.298(4) A, Z=6, μ = 0. 856mm- 1, R=0. 0671, w R = 0. 1661 for complex 2. They are of 18-azametallacrown-6 structure type. The metallacrown molecules in two title complexes have a crystallographic C3i symmetry. The triple-deprotonated ligand ashz3- in the title complexes bridges the metal ions by a hydrazide N-N group, forming a hexanuclear manganese metallmacrocycle with a cavity in the center. The magnetic susceptibility (4 ～ 275K) study indicates that there is an antiferromagnetic exchange interaction in the title compound 1. CCDC: 192835(complex 1); 192836(complex 2).