Four Novel d10 Metal-Organic Frameworks Incorporating Amino-Functionalized Carboxylate Ligands: Synthesis, Structures, and Fluorescence Properties

Wang Xie; Jie Wu; Xiaochun Hang; Honghai Zhang; Kang Shen; Zhoulu Wang

doi:10.3389/fchem.2021.708314

Four Novel d¹⁰ Metal-Organic Frameworks Incorporating Amino-Functionalized Carboxylate Ligands: Synthesis, Structures, and Fluorescence Properties

Front Chem. 2021 Aug 30:9:708314. doi: 10.3389/fchem.2021.708314. eCollection 2021.

Authors

Wang Xie¹, Jie Wu¹, Xiaochun Hang¹, Honghai Zhang¹, Kang Shen^{1

2}, Zhoulu Wang¹

Affiliations

¹ Key Laboratory of Flexible Electronics & Institute of Advanced Materials, Jiangsu National Synergistic Innovation Center for Advanced Materials, School of Energy Science and Engineering, Nanjing Tech University, Nanjing, China.
² State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, China.

Abstract

By employment of amino-functionalized dicarboxylate ligands to react with d¹⁰ metal ions, four novel metal-organic frameworks (MOFs) were obtained with the formula of {[Cd(BCPAB)(μ ₂-H₂O)]} _n (1), {[Cd(BDAB)]∙2H₂O∙DMF} _n (2), {[Zn(BDAB)(BPD)_0.5(H₂O)]∙2H₂O} _n (3) and {[Zn(BDAB)(DBPB)_0.5(H₂O)]∙2H₂O} _n (4) (H₂BCPAB = 2,5-bis(p-carbonylphenyl)-1-aminobenzene; H₂BDAB = 1,2-diamino-3,6-bis(4-carboxyphenyl)benzene); BPD = (4,4'-bipyridine); DBPB = (E,E-2,5-dimethoxy-1,4-bis-[2-pyridin-vinyl]-benzene; DMF = N,N-dimethylformamide). Complex 1 is a three-dimensional (3D) framework bearing seh-3,5-Pbca nets with point symbol of {4.6²}{4.6⁷.8²}. Complex 2 exhibits a 4,4-connected new topology that has never been reported before with point symbol of {4².8⁴}. Complex 3 and 4 are quite similar in structure and both have 3D supramolecular frameworks formed by 6-fold and 8-fold interpenetrated 2D coordination layers. The structures of these complexes were characterized by single crystal X-ray diffraction (SC-XRD), thermal gravimetric analysis (TGA) and powder X-ray diffraction (PXRD) measurements. In addition, the fluorescence properties and the sensing capability of 2-4 were investigated as well and the results indicated that complex 2 could function as sensor for Cu²⁺ and complex 3 could detect Cu²⁺ and Ag⁺ via quenching effect.

Keywords: amino groups; d10 -metal ions; detection; fluorescence; metal-organic frameworks.