Diversity of Coordination Architecture of Copper(II)−5-Sulfoisophthalic Acid: Synthesis, Crystal Structures, and Characterization

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Abstract

Hydrothermal synthesis of a series of copper(II)−H3SIP coordination polymers (H3SIP = 5-sulfoisophthalic acid), [Cu3(SIP)2(H2O)14] (1), {[Cu(SIP)(H2O)4](H2en)0.5}n (2), {Na[Cu2(SIP)(HSIP)(H2O)8](H2O)3}n (3), {[Cu4(OH)2(SIP)2(H2O)2](H2O)4}n (4), [Cu2(OH)(SIP)(bpy)(H2O)]n (5), [Cu4(OH)2(SIP)2(bpy)3(H2O)]n (6), and [Cu4(OH)2(SIP)2(bpy)2(H2O)2]n (7) (bpy = 2,2‘-bipyridine; en = ethylenediamine), has been achieved by fine control over the reaction conditions including pH value, organic template, reaction temperature, starting materials, auxiliary ligand, and stoichiometry. X-ray structural analyses of 1−7 reveal their structural diversity ranging from zero-dimensional (0-D) (1), one-dimensional (1-D) (2), two-dimensional (2-D) (3, 5, and 6), to three-dimensional (3-D) (4 and 7). The relationship between the reaction conditions and the resulting structures has been rationalized. The trinuclear complex 1 represents the first example of a discrete metal−SIP coordination complex. The presence of countercations such as H2en2+ and Na+ leads to the formation of a Cu−SIP zigzag chain in 2 and 3. A larger template such as triethylenediamine (TEDA) accounts for the formation of the tetranuclear [Cu4(μ3-OH)2] secondary building unit (SBU) in 4 and hence the 3-D network structure with unprecedented (411·614·83)(45·6)2 topology. Polymer 5 formed at a comparatively lower temperature has the binuclear [Cu2(μ2-OH)] SBU and thus the 2-D double-sided layer structure of 4·82 topology. The enhanced temperature results in the formation of the tetranuclear [Cu4(μ3-OH)2] SBU of 7 and hence the 3-D framework structure of rutile topology (4·62)2(42·610·83). 6 contains the unusual tetranuclear [Cu4(μ3-OH)(μ2-OH)] SBU induced by one more bpy ligand that results in a 2-D layered structure of unique (3·52)2(32·53) topology. The temperature-dependent magnetic susceptibility data of 1−5 have been modeled using both Curie−Weiss law and isotropic spin-Hamiltonian, revealing weakly ferromagnetically or antiferromagnetically magnetic interactions between the Cu2+ ions bridged by OH- or SIP ligands.

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