Structure and magnetism of a porous three-dimensional metal-organic framework based on planar tetranuclear copper(II) cluster units

Abstract

A porous three-dimensional copper(II) metal-organic framework (MOF) {[Cu 2 (tci)(OH)(pip) 0.5 (H 2 O)]·6H 2 O} n (1) [tci = tris (2-carboxyethyl)isocyanurate, pip = piperazine] has been generated under hydrothermal conditions at 120 °C. Single crystal X-ray diffraction reveals that the polymer exhibits a novel three-dimensional framework based on planar tetranuclear copper(II) cluster units. The variable temperature magnetic susceptibility data in the range 2-280 K show antiferromagnetic spin-spin coupling in the tetranuclear unit in complex 1. A theoretical fitting of the magnetic data gives J values of 31.3 cm 1 , 30.8 cm 1 , and 13.5 cm 1 . metal-organic framework, tetranuclear copper cluster unit, topology, magnetism

Multinuclear Cu(I) Clusters Featuring a New Triply Bridging Coordination Mode of Phosphaamidinate Ligands

“…The literature includes reports of a variety of tetranuclear Cu(II) and Cu(I) assemblies. The Cu(II) structures include chairlike K , 30 linear L , 31 tetrahedral M , 32 and planar N 33 geometries (Figure 4). Most of them are held together by bridging O or N atoms.…”

Structure and Magnetic Properties of a 2D Paddle‐wheel Dinuclear[Cu2] Cluster‐based Polymer with 1,1‐Cyclohexanediacetate Ligand

“…In particular, a large and diverse group of magnetic materials have been built from copper(II) with carboxylic acids, which may be not only due to the paramagnetic copper(II) ions presenting varied coordination numbers and more flexible coordination modes but also to carboxylate group in the carboxylic acids, which can adopt various coordination modes and offer superexchange pathways to transfer interactions between copper ions , . The reported literatures about copper magnets are mainly focus on discrete copper(II) clusters such as dinuclear, trinuclear, and tetranuclear, as well as uniform copper chains, and the multidimensional MCPs with the multinuclear copper(II) clusters as secondary building units (SBUs) are still limited reported, although they may display more versatile topological structure and interesting magnetic properties , …”

A 2-D Metal–Organic Framework Based on Linear Trinuclear Copper Cluster Units: Syntheses, Structures and Magnetic Properties

“…7,8 As a flexible tripodal ligand, 1,3,5-tris(2-carboxyethyl) isocyanurate (H 3 tci) is a good candidate for designing diverse MOFs due to its three -CH 2 CH 2 COOH arms, which give conformational flexibility, and its three freely rotatable carboxyl groups with different configurations and diverse coordination modes via oxygen donors. [9][10][11][12][13][14][15][16][17] The carboxyl groups of the flexible methylacetate units can connect with metal ions to form polynuclear metal cluster units, such as triangular, tetrahedral, trigonal prismatic, octahedral and planar tetracopper molecular building units. [11][12][13][14][15][16] Such units can be regarded as nodes, and tripodal skeletons link these nodes, resulting in diverse MOFs that vary from discrete molecules to infinite networks.…”

“…[9][10][11][12][13][14][15][16][17] The carboxyl groups of the flexible methylacetate units can connect with metal ions to form polynuclear metal cluster units, such as triangular, tetrahedral, trigonal prismatic, octahedral and planar tetracopper molecular building units. [11][12][13][14][15][16] Such units can be regarded as nodes, and tripodal skeletons link these nodes, resulting in diverse MOFs that vary from discrete molecules to infinite networks. [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] At present, H 3 tci has not been well explored in comparison with other tripodal carboxylic acid ligands, such as 1,3,5-tris(4carboxyphenyl) benzene and 1,3,5-benzenetricarboxylic acid.…”