基于N,N'-双(3-吡啶基)-对苯二甲酰胺和1,3,5-苯三甲酸的二维Co(Ⅱ)金属有机骨架的合成、结构和磁性

doi:10.11944/j.issn.1000-0518.2019.12.190125

摘要/Abstract

摘要：

在水热条件下,基于配体N,N'-双(3-吡啶基)-对苯二甲酰胺(3-bptpa)和1,3,5-苯三甲酸(1,3,5-H₃btc),合成了一例具有二维格子结构的钴(Ⅱ)MOF[Co(3-bptpa)(1,3,5-Hbtc)]·2H₂O(1),并进行了红外光谱(FT-IR)、元素分析(EDS)、差热-热重分析(DTA-TG)、X射线单晶衍射(XRD)和磁学表征。结果表明,每个1,3,5-Hbtc^2-提供1个螯合配位羧基和1个桥连配位羧基与Co(Ⅱ)离子配位。中心对称的二聚体[Co(3-bptpa)(1,3,5-Hbtc)]₂通过桥连配位的羧基连接成1D梯形链,相邻的梯形链通过3-bptpa与Co(Ⅱ)的配位作用连接为2D格子,从而形成CoN₂O₄变形八面体的配位构型。对配合物1在16~300 K的磁化率数据,使用八面体场下旋轨耦合的各向同性的单离子近似和分子场理论进行分析,Co(Ⅱ)离子表现强的旋轨耦合作用(λ=-100.4 cm^-1),相邻的Co(Ⅱ)离子之间通过桥连配位的羧基传递弱的反铁磁相互作用(zj'=-0.618 cm^-1)。

关键词: 二吡啶二酰胺配体, 水热合成, 钴(Ⅱ);, 金属-有机骨架, 磁性

Abstract:

Based on N,N'-bis-(3-pyridyl)terephthalamide (3-bptpa) and 1,3,5-benzenetricarboxylic acid (1,3,5-H₃btc), a Co(Ⅱ) metal-organic framework [Co(3-bptpa)(1,3,5-Hbtc)]·2H₂O(1) with a 2D grid-like structure was hydrothermally synthesized. Complex 1 was characterized by X-ray crystallography, Fourier transform infrared (FT-IR) spectra, elemental analysis, thermal analysis and magnetic measurements. Each 1,3,5-Hbtc^2- provided one chelating and one bridging carboxylate groups to coordinate to Co(Ⅱ) cations. The centrosymmetric dimer [Co(3-bptpa)(1,3,5-Hbtc)]₂ was assembled into a 1D ladder-like chains by bridging carboxylate groups. The neighbouring chains were connected into 2D grid-like network by the coordination of 3-bptpa to Co(Ⅱ), resulting in the distorted CoN₂O₄ octahedral coordination sphere. The magnetic data of complex 1 in the temperature range 16~300 K were analyzed including the one-ion approximation for Co(Ⅱ) with spin-orbit coupling in O_h symmetry and intermolecular exchange interaction(zj') in the molecular field approximation leading to λ=-100.4 cm^-1 and zj'=-0.618 cm^-1. CCDC:1910964

Key words: dipyridine diamide ligand, hydrothermal synthesis, cobalt(Ⅱ);, metal-organic framework(MOF), magnetic properties

王琦, 仝玉章, 贾晓普, 杨春, 王庆伦, 廖代正. 基于N,N'-双(3-吡啶基)-对苯二甲酰胺和1,3,5-苯三甲酸的二维Co(Ⅱ)金属有机骨架的合成、结构和磁性[J]. 应用化学, 2019, 36(12): 1397-1405.

WANG Qi, TONG Yuzhang, JIA Xiaopu, YANG Chun, WANG Qinglun, LIAO Daizheng. Syntheses, Crystal Structures and Magnetic Properties of a 2D Cobalt(Ⅱ) Metal-Organic Framework Based on N,N'-Bis-(3-Pyridyl) Terephthalamide and 1,3,5-Benzenetricarboxylic Acid[J]. Chinese Journal of Applied Chemistry, 2019, 36(12): 1397-1405.

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