萘基二膦酸钴配合物的合成、晶体结构和磁性质

人工晶体学报 ›› 2022, Vol. 51 ›› Issue (7): 1233-1240.

萘基二膦酸钴配合物的合成、晶体结构和磁性质

徐艳, 崔磊, 李新星, 吉玉如, 王楠, 王宣, 王肖阳, 高文康

宿迁学院信息工程学院,材料工程系,宿迁 223800

收稿日期:2022-03-23 出版日期:2022-07-15 发布日期:2022-08-11
通讯作者: 崔磊,教授。E-mail:16077@squedu.cn
作者简介:徐艳(1983—),女,江苏省人,博士,副教授。E-mail:xuyan0511@126.com
基金资助:
宿迁市科技计划(K201911);宿迁市高性能复合材料重点实验室(M202109);宿迁学院多功能材料研发平台(2021pt04);宿迁学院科研创新团队(2021td01);宿迁学院西楚学者项目

Synthesis, Crystal Structure and Magnetic Properties of Naphthalene-Based Cobalt Diphosphonates Compound

XU Yan, CUI Lei, LI Xinxing, JI Yuru, WANG Nan, WANG Xuan, WANG Xiaoyang, GAO Wenkang

Department of Materials Engineering, Institute of Information Engineering, Suqian University, Suqian 223800, China

Received:2022-03-23 Online:2022-07-15 Published:2022-08-11

摘要/Abstract

摘要： 基于萘二膦酸,采用水热法合成两例新型钴配合物[Co₄(1,4-ndpa)₂(4,4′-bpy)₂]·5H₂O (1)和[Co(1,4-ndpaH)]·1.5H₂O (2),其中1,4-ndpa^4-为1,4-萘二膦酸去质子化,4,4′-bpy为4,4′-联吡啶。在配合物1和2中,钴原子呈四配位的畸变四面体构型。配合物1的晶体结构中包含有共用顶点的四面体{CoNO₃}和{PO₃C}的梯形链,这些梯形链分别由1,4-ndpa^4-和4,4′-bpy配体与相邻的梯形链连接,形成开放的三维框架结构,结晶水分子通过氢键作用填充在骨架的空隙中。配合物2的晶体结构中包含有不同于配合物1的链结构,共用顶点四面体{CoO₄}和{PO₃C}组成的无机链仅通过1,4-ndpaH^3-配体交联形成三维开放框架结构。磁性研究表明,配合物1中Co^II存在自旋轨道耦合和/或Co^II之间存在反铁磁相互作用。

关键词: 金属-有机框架, 水热法, 钴膦酸盐, 晶体结构, 磁性质

Abstract: Two new cobalt diphosphonates with formulae [Co₄(1,4-ndpa)₂(4,4′-bpy)₂]·5H₂O (1) and [Co(1,4-ndpaH)]·1.5H₂O (2) are isolated based on naphthalene scaffold, where 1,4-ndpa^4- represents deprotonation of 1,4-naphthalene diphosphonic acid and 4,4′-bpy is 4,4′-bipyridine. The cobalt atoms are four coordinated with distorted tetrahedral geometries in both 1 and 2. Compound 1 displays a three dimensional framework structure containing ladder-like chains made up of corner-sharing tetrahedra {CoNO₃} and {PO₃C}. These ladder-like chains are then connected with adjacent ladder-like chains through 1,4-ndpa^4-and 4,4′-bpy ligands respectively. Lattice water molecules fill the gaps in the skeleton by hydrogen bond. Compound 2 has a different type of chain structure, where the inorganic chains composed of corner-sharing {CoO₄} and {PO₃C} are cross-linked by only 1,4-ndpaH^3- ligands into 3D open framework structures. Magnetic studies reveal that spin-orbit coupling and/or antiferromagnetic interaction of Co^II is observed in compound 1.

Key words: metal-organic framework, hydrothermal method, cobalt phosphonate, crystal structure, magnetic property

中图分类号:

O641.4

徐艳, 崔磊, 李新星, 吉玉如, 王楠, 王宣, 王肖阳, 高文康. 萘基二膦酸钴配合物的合成、晶体结构和磁性质[J]. 人工晶体学报, 2022, 51(7): 1233-1240.

XU Yan, CUI Lei, LI Xinxing, JI Yuru, WANG Nan, WANG Xuan, WANG Xiaoyang, GAO Wenkang. Synthesis, Crystal Structure and Magnetic Properties of Naphthalene-Based Cobalt Diphosphonates Compound[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(7): 1233-1240.

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