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Synthesis, Structures, and Sorption Properties of Two New Metal-Organic Frameworks Constructed by the Polycarboxylate Ligand Derived from Cyclotriphosphazene.

ABSTRACT: Solvothermal reactions of hexakis(4-carboxyphenoxy)cyclotriphospazene (H₆L1) with copper ions in DMF/H₂O produced one complex, {[Cu₆(L1)₂(OH)(H₂O)₃]·guest} _n (1), but with copper ions and auxiliary rigid 4,4-bipyridine (bpy) produced another new complex, namely, {[Cu₃(L1)(bpy)(H₂O)₆]·guest} _n (2). These complexes had been characterized by IR spectroscopy, elemental analysis, and X-ray structural determination. 1 exhibits a 3D anionic structure with the binodal 4,8-connected network with Schläfli symbol {4⁶}₂{4⁹·6¹⁸·8}, consisting of Cu₆ clusters and L1 ligands. In contrast, complex 2 possesses a different 3D network with trinodal 3,4,6-c topology with Schläfli symbol {4·6²}₂{4²·6⁶·8⁵·10²}{6⁴·8·10}. In these two complexes, the semirigid hexacarboxylate ligands adopt distinct conformations to connect metal ions/clusters, which must be ascribed to the addition of the auxiliary rigid ligand in reaction systems. In addition, gas absorption properties of 1 and 2 including CO₂ and N₂ were further investigated.

SUBMITTER: Han JH

PROVIDER: S-EPMC8444217 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

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Synthesis, Structures, and Sorption Properties of Two New Metal-Organic Frameworks Constructed by the Polycarboxylate Ligand Derived from Cyclotriphosphazene.

Han Jing-Hua JH Hu Bing-Qian BQ Li Tangming T Liang Hao H Yu Fan F Zhao Qiang Q Li Bao B

ACS omega 20210902 36

Solvothermal reactions of hexakis(4-carboxyphenoxy)cyclotriphospazene (H6L1) with copper ions in DMF/H2O produced one complex, {[Cu6(L1)2(OH)(H2O)3]·guest} n (1), but with copper ions and auxiliary rigid 4,4-bipyridine (bpy) produced another new complex, namely, {[Cu3(L1)(bpy)(H2O)6]·guest} n (2). These complexes had been characterized by IR spectro ...[more]

PMID: 34549112

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Project description:Three novel complexes of formula [Co(5)(OH)(2)(cht)(2)(H(2)O)(10)](n) x 2nH(2)O (1) (H(4)cht = cyclohexane-1,2,4,5-tetracarboxylic acid), [Zn(2)(cht)(H(2)O)(3)](n) x nH(2)O (2), and [Cd(2)(cht)(H(2)O)(5)](n) x 2nH(2)O (3) were synthesized by a hydrothermal reaction of cyclohexane-1,2,4,5-tetracarboxylic acid in the presence of sodium hydroxide with Co(NO(3))(2) x 6H(2)O, Zn(NO(3))(2) x 6H(2)O, and Cd(NO(3))(2) x 4H(2)O, respectively. These complexes were obtained by controlling the molar ratios of starting materials and the pH values of reaction mixtures with an initial pH of 5.87 for 1, 5.50 for 2, and 5.57 for 3, respectively. The single-crystal X-ray investigations reveal that the cht ligands change their conformations exclusively to the a,e,e,a form in all three complexes. Complex 1 features a two-dimensional (2D) metal-organic framework (MOF) with an axis surrounded by two zigzag structures, a rectangular channel surrounded by two a-carboxylate-metal-a-carboxlate and two e-carboxylate-metal-e-carboxylate chains, and two smaller distorted square-pyramidal channels surrounded by hydroxyl oxygen, cyclohexane, and its two a-carboxylates. Each cht ligand connects five cobalt atoms and each cobalt atom is six-coordinated with carboxylate-oxygen, hydroxyl, and water molecules. Complex 2 possesses a three-dimensional (3D) MOF structure that consists of the cht ligands and two types of cobalt; one is four-coordinated with carboxylate-oxygens and the other is six-coordinated with carboxylate-oxygens and water molecules. Each cht ligand is bonded to seven zinc atoms. Complex 3 is also a 2D MOF structure constructed by seven-coordinated cadmium atoms and the cht ligands. The e-carboxylates of two parallel cht ligands are connected to a type of cadmium atoms to form 1D chains, and these chains are further connected through a-carboxylates of the ligands and another type of cadmium atoms to give the 2D structure. Extensive hydrogen bonding interactions involving carboxylate-oxygen atoms and crystallization water molecules afford 3D supramolecular networks in complexes 1 and 2. Magnetic susceptibility measurement of 1 confirmed a six-coordinated high-spin cobalt(II) ion and the presence of magnetic exchange coupling among the three hydroxyl-oxygen bridged cobalt ions. Fluorescent spectra of complexes 2 and 3 show strong fluorescent emissions in the blue region.

Dataset Information

Synthesis, Structures, and Sorption Properties of Two New Metal-Organic Frameworks Constructed by the Polycarboxylate Ligand Derived from Cyclotriphosphazene.

Publications

Synthesis, Structures, and Sorption Properties of Two New Metal-Organic Frameworks Constructed by the Polycarboxylate Ligand Derived from Cyclotriphosphazene.

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