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Construction of fluorescence active MOFs with symmetrical and conformationally rigid N-2-aryl-triazole ligands.

ABSTRACT: 1,4-Bis-triazole-substituted arene (NAT) was designed and synthesized for the construction of metal organic frameworks. Unlike the tri-phenyl analogs, which give a twisted conformation between three benzene rings due to the A-1,3 repulsion, the NAT-ligand gave the energetically favored co-planar conformation with the strong fluorescence emission. With this ligand, two new MOFs, NAT-MOF-Cd (2,3,4-c) and NAT-MOF-Cu (4-c), were successfully obtained with the structure confirmed by X-ray. With the six-coordinated Cd(ii) cluster, an interesting metal-ligand coordination and H-bonding hybridized porous polymeric structures were observed. In contrast, a typical Cu(ii) paddle wheel coordination was obtained with NAT and Cu, giving a new MOF structure with moderate stability in aqueous solution from pH 1-11 for 24 hours, which suggests a promising future for applications in fluorescence sensing and photocatalysis.

SUBMITTER: Li J

PROVIDER: S-EPMC9057867 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Construction of fluorescence active MOFs with symmetrical and conformationally rigid <i>N</i>-2-aryl-triazole ligands.

Li Jingyang J He Ying Y Wang Li L Li Guanghua G Zou Yongcun Y Yan Yan Y Li Dandan D Shi Xinli X Song Zhiguang Z Shi Xiaodong X

RSC advances 20201118 68

1,4-Bis-triazole-substituted arene (NAT) was designed and synthesized for the construction of metal organic frameworks. Unlike the tri-phenyl analogs, which give a twisted conformation between three benzene rings due to the A-1,3 repulsion, the NAT-ligand gave the energetically favored co-planar conformation with the strong fluorescence emission. With this ligand, two new MOFs, NAT-MOF-Cd (2,3,4-c) and NAT-MOF-Cu (4-c), were successfully obtained with the structure confirmed by X-ray. With the s ...[more]

PMID: 35516574

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Project description:Five new polyoxometalate (POM)-based metal-organic complexes (MOCs) with different rigid pyridyl-bis(triazole) ligands, namely, H{Co2(Hpyttz-I)2(H2O)6[CrMo6(OH)6O18]}·8H2O (1), {Co2(H2pyttz-I)2(H2O)4[TeMo6O24]}[Co(H2O)6]·3H2O (2), {Co3(Hpyttz-II)2(H2O)6[γ-Mo8O26]}·10H2O (3), {Ni3(Hpyttz-II)2(H2O)6[γ-Mo8O26]}·10H2O (4), {Ni3(Hpyttz-III)2(H2O)8[γ-Mo8O26]}·10H2O (5) (H2pyttz-I = 3-(pyrid-2-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl, H2pyttz-II = 3-(pyrid-3-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl, H2pyttz -III = 3-(pyrid-4-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl), were successfully synthesized and structurally characterized by single-crystal X-ray diffraction, IR spectra, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Complex 1 is a two-dimensional (2D) supramolecular network based on the binuclear complex unit: [Co2(Hpyttz-I)2(H2O)6 [CrMo6(OH)6O18]]. Complex 2 is a 1D supramolecular chain derived from the binuclear cobalt complex: {Co2(H2pyttz-I)2(H2O)4[TeMo6O24]}2-, the discrete [Co(H2O)6]2+ units act as counter cations. Complexes 3 and 4 are isostructural with different center metals (M = Co or Ni), the adjacent γ-Mo8O26 4- anions are linked by the MII ions to form a 1D M-γ-Mo8O26 inorganic chain. Then 1D M-γ-Mo8O26 inorganic chains are linked together by the 1D metal-organic M-(Hpyttz-II) chains to form a 3D framework. In complex 5, γ-Mo8O26 4- anions are bridged by the NiII ions to give a 1D Ni-γ-Mo8O26 inorganic chain, the adjacent 1D Ni-γ-Mo8O26 chains are connected through [Ni(Hpyttz-III)2] units to form a 2D layer. The effect of POM type and coordination site of the ligands on the structures of the title complexes were discussed. The title complexes 1, 2 and 5 exhibit excellent bifunctional electrocatalytic activities toward the reduction of bromate/hydrogen peroxide and the oxidation of ascorbic acid. In addition, the redox potentials of complexes 1, 2 and 5 are highly sensitive to pH and may be used as a kind of potential pH sensor.

Dataset Information

Construction of fluorescence active MOFs with symmetrical and conformationally rigid N-2-aryl-triazole ligands.

Publications

Construction of fluorescence active MOFs with symmetrical and conformationally rigid <i>N</i>-2-aryl-triazole ligands.

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