O-P-O桥联锰-席夫碱配合物的合成、结构和磁性质  

O-P-O bridged Mn^(Ⅲ)‑Schiff base complexes:Syntheses,structures,and magnetic properties

作　　者：徐艳[1] 刘照文[1] 崔磊[1] XU Yan;LIU Zhao-Wen;CUI Lei(Department of Materials Engineering,Suqian University,Suqian,Jiangsu 223800,China)

机构地区：[1]宿迁学院信息工程学院材料工程系,宿迁223800

出　　处：《无机化学学报》2023年第8期1628-1636,共9页Chinese Journal of Inorganic Chemistry

基　　金：江苏省青蓝工程、宿迁学院科研平台(2021pt04);宿迁学院西楚高层次人才和宿迁市重点实验室(No.M202109)基金资助。

摘　　要：采用溶液法合成了2例由O-P-O单元桥联的锰-席夫碱(SB)新型三核配合物,即[Mn_(3)(salen)_(3)(L)]ClO_(4)·H_(2)O (1)和[Mn_(3)(salpn)_(3)(L)]ClO_(4)(2),其中salen2-=N,N′-乙二胺缩双水杨醛,salpn^(2-)=N,N′-丙二胺缩双水杨醛,H2L=(5-(乙氧基羰基)萘-1-基)膦酸。通过单晶X射线衍射、红外光谱、粉末X射线衍射对其进行了表征。配合物1和2是同构的,均是由膦酸酯配体中的O-P-O桥联3个[Mn(SB)]+构成一个三核结构单元[Mn3(SB)3(L)]+,一个无序的ClO_(4)^(-)作为平衡阴离子存在。这些[Mn_(3)(SB)_(3)(L)]+三聚体通过π-π相互作用和相邻的分子形成超分子一维波形链。配合物1和2的磁性研究表明,不对称结构中的3个Mn离子分别是2个高自旋和1个低自旋,而Mn离子之间主要存在反铁磁相互作用。Two new trinuclear complexes consisting of Mn^(Ⅲ)-Schiff base(SB)building block bridged by O-P-O units,namely[Mn_(3)(salen)_(3)(L)]ClO_(4)·H_(2)O(1)and[Mn_(3)(salpn)3(L)]ClO_(4)(2),where salen2-=N,N′-(ethylene)bis(salicyli-deneiminato),salpn2-=N,N′-(propylene)bis(salicylideneiminato),H_(2)L=5-(ethoxycarbonyl)-(naphthalen-1-yl)phosphon-ic acid,were synthesized by using solvent evaporation and characterized by using single-crystal X-ray diffraction,IR,and powder X-ray diffraction.Complexes 1 and 2 are isostructural and show similar trinuclear[Mn_(3)(SB)_(3)(L)]+,in which O-P-O groups among the phosphonate ligand bridge three Mn􀃮ion centers,and an additional disordered ClO_(4)-as a balance anion.These[Mn3(SB)3(L)]+trimers are assembled byπ-πinteraction from the neighboring com-plexes,giving rise to a supramolecular 1D wave chain.Magnetic measurements of 1 and 2 indicate that the three Mn􀃮ions in the asymmetric structure are two with high spin and one with low spin,while dominant antiferromag-netic interactions are mediated between the Mn􀃮ions.CCDC:2240031,1;2058378,2.

关 键 词：锰-席夫碱 萘膦酸酯配体 晶体结构 磁性质 

分 类 号：O614.711[理学—无机化学]