锰有机膦酸配位聚合物的合成、结构和磁性  

Syntheses,Structures and Magnetic Properties of Manganese Phosphonates

作　　者：刘蓓 鲍松松 任旻[1] 蔡中胜 刘景翠 郑丽敏[1] LIU Bei;BAO Song-Song;REN Min;CAI Zhong-Sheng;LIU Jing-Cui;ZHENG Li-Min(State Key Laboratory of Coordination Chemistry,School of Chemistry and Chemical Engineering,Nanjing University,Nanjing 210023,China)

机构地区：[1]南京大学化学化工学院,配位化学国家重点实验,南京210023

出　　处：《无机化学学报》2020年第6期1185-1194,共10页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21731003)资助项目。

摘　　要：将4-羧酸-1-萘膦酸(4-cnapp H3)与氯化锰通过水热(溶剂热)反应,得到4种不同结构的锰萘膦酸羧酸配位聚合物Mn(4-cnapp H2)2(1),Mn(4-cnapp H2)2(H2O)2(2),α-Mn(4-cnapp H)(H2O)(3)和β-Mn(4-cnapp H)(H2O)(4)。化合物1中{Mn O6}八面体与{PO3C}四面体共角连接形成无机链,链与链之间通过膦酸配体连接形成三维框架结构,而化合物2~4都具有层状结构,层与层之间由质子化的羧酸基团通过氢键作用连接形成三维超分子结构。但这些化合物的层内拓扑结构不同,化合物2中的无机层结构包含由{Mn O6}八面体和{PO3C}四面体共角连接的矩形12元环,化合物3中{Mn O5}三角双锥共边形成{Mn2O2}双核,双核之间通过{PO3C}四面体共角连接形成包含4元环的无机层,而化合物4中则存在由{Mn O5}三角双锥共角形成的链,链间进一步通过{PO3C}四面体共角连接形成包含3元环和4元环的无机层。磁性研究表明,所有化合物中锰离子之间都存在反铁磁相互作用。Reactions of(4-carboxynaphthalen-1-yl)phosphonic acid(4-cnapp H3)with manganese chloride under solvo/hydrothermal conditions resulted in four new coordination polymers,formulated as Mn(4-cnapp H2)2(1),Mn(4-cnapp H2)2(H2O)2(2),α-Mn(4-cnapp H)(H2O)(3)andβ-Mn(4-cnapp H)(H2O)(4).Compound 1 shows a 3D framework structure,where chains made up of corner-sharing{Mn O6}octahedra and{PO3C}tetrahedra are cross-linked by the organic groups of the phosphonate ligands.Compounds 2~4 exhibit 2D layered structures with interlayer hydrogen bonds through the pendent carboxylic acid groups.However,the layer topologies are different in the three cases.In 2,the{Mn O6}octahedra and{PO3C}tetrahedra are corner-shared with each other alternatively,forming an inorganic layer containing rectangular-shaped 12-membered rings.In 3,edge-sharing dimers of{Mn2O2}are connected by{PO3C}tetrahedra through corner-sharing,forming an inorganic layer containing 4-membered rings.In 4,chains of corner-sharing{Mn O5}are connected by{PO3C}tetrahedra into an inorganic layer containing 3-and 4-membered rings.Magnetic studies reveal that antiferromagnetic interactions are dominant in all four compounds.CCDC:1990441,1;1990442,2;1990443,3;1990444,4.

关 键 词：有机膦酸 锰配合物 配位聚合物 层状 磁性 

分 类 号：O614.711[理学—无机化学]