Introducing 2-(2-carboxyphenoxy)terephthalic acid as a new versatile building block for design of diverse coordination polymers: synthesis, structural features, luminescence sensing, and magnetism

Abstract

In this work, an ether-bridged aromatic carboxylic acid, 2-(2-carboxyphenoxy)terephthalic acid (H3cpta), was applied as an unexplored building block for the generation of a novel series of coordination compounds, which represent the first examples of structurally characterized products derived from H3cpta, thus opening up its use as a versatile building block in crystal engineering research. The obtained products were formulated as [Cd(μ-Hcpta)(phen)(H2O)]n (1), [Mn(μ-Hcpta)(phen)(H2O)]n (2), {[Cd3(μ3-Hcpta)(μ4-cpta)(μ-Cl)(H2O)4]·2H2O}n (3), {[Cd3(μ6-cpta)2(py)2]·5H2O}n (4), [Mn3(μ5-cpta)2(2,2′-bipy)2]n (5), [Mn3(μ4-cpta)2(phen)3(H2O)2]n (6), {[Zn3(μ3-cpta)2(phen)3]·3H2O} (7), [Cd2(μ4-cpta)(μ-Cl)(phen)2]n (8), [Cd3(μ5-cpta)2(phen)2(H2O)2]n (9), [Cd3(μ4-cpta)2(phen)3(H2O)2]n (10), [Cd3(μ5-cpta)2(H2biim)2]n (11), [Zn2(μ6-cpta)(μ-Hbiim)]n (12), and [Ni3(μ3-cpta)2(phen)3(py)3(H2O)3]n (13). These compounds were assembled in the presence of an optional N-donor ancillary ligand, which was selected from 1,10-phenanthroline (phen), pyridine (py), 2,2′-bipyridine (2,2′-bipy), or 2,2′-biimidazole (H2biim). The obtained compounds 1–13 were fully characterized, including by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder (PXRD) and single-crystal X-ray diffraction. The structures of 1–13 vary from a discrete 0D dimer (1) to the 1D (2, 3, 7, and 13) and 2D (5, 6, and 8–11) coordination polymers, as well as to the 3D metal–organic frameworks (MOFs 4 and 12). Such a wide structural diversity of 1–13 is guided by the following factors: a type of metal(II) node and counter anion, a deprotonation degree of the principal H3cpta block, and/or a type of an auxiliary ligand. Topological classification of H-bonded (in 1) and metal–organic (in 2–13) underlying networks was performed, disclosing the following topological types: sql (in 1), 2C1 (in 2 and 7), 3,4,5L45 (in 5, 9, and 11), 3,4L128 (in 6 and 10), 3,3,4L29 (in 8), and SP 1-periodic net (in 13), as well as some topologically unique nets (in 3, 4, and 12). Besides, magnetic properties of 2, 5, 6, and 13 were studied and modeled, revealing antiferromagnetic interactions between adjacent metal(II) centers. In addition, luminescence properties were investigated for 1, 3, 4, and 7–12; MOF 4 can be used as a sensitive material for the detection of Fe3+ ions in aqueous solution through the luminescence quenching effect.