New Zn(II) Coordination Polymers Constructed from Amino-Alcohols and Aromatic Dicarboxylic Acids: Synthesis, Structure, Photocatalytic Properties, and Solid-State Conversion to ZnO

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• 作者：Carmen Paraschiv ; Andrei Cucos ; Sergiu Shova ; Augustin M. Madalan ; Catalin Maxim ; Diana Visinescu ; Bogdan Cojocaru ; Vasile I. Parvulescu ; Marius Andruh
• 刊名：Crystal Growth & Design
• 出版年：2015
• 出版时间：February 4, 2015
• 年：2015
• 卷：15
• 期：2
• 页码：799-811
• 全文大小：817K
• ISSN：1528-7505

文摘

Four new coordination polymers have been obtained solvothermally from the reactions of Zn(NO₃)₂路6H₂O with 1,2-, 1,3-, or 1,4-benzedicarboxylic acids in the presence of various amino-alcohols: ₁^{鈭?/sup>[Zn₂(Htea)₂(1,2-bdc)] (1), ₁鈭?/sup>[Zn(H₃tris)(1,3-bdc)(CH₃OH)] (2), ₃鈭?/sup>[Zn₅(Htea)₂(1,3-bdc)₃(H₂O)]路2.6H₂O (3), and ₃鈭?/sup>[Zn₃(H₂dea)₂(1,4-bdc)₃] (4) (H₃tea = triethanolamine, H₃tris = tris(hydroxymethyl)aminomethane, H₂dea = diethanolamine, 1,2-H₂bdc =1,2-benzenedicarboxylic acid, 1,3-H₂bdc =1,3-benzenedicarboxylic acid, and 1,4-H₂bdc =1,4-benzenedicarboxylic acid). Their crystal structures, thermogravimetric analyses, solid-state transformation to ZnO and characterization of the resultant zinc oxide particles are reported. Compounds 1 and 2 show three-dimensional (3D) supramolecular architectures, generated from the interconnection of the zigzag (in 1) and respectively the linear (in 2) chains through hydrogen bonding interactions. The crystal structure of 3 revealed the presence of five different types of zinc atoms that are successively linked through carboxilato or alkoxo bridges in a helicoidal chain running along the crystallographic a axis. Both right-handed (P) and left-handed (M) helices are present in the crystal, and they are alternately interconnected by pairs of isophthalato bridges, resulting in channels of hexagonal shape, filled with water molecules. Compound 4 has a 3D structure in which linear centrosymmetric {Zn₃(H₂dea)₂}6+ nodes are joined by terephthalate bridges. Owing to its porous network, compound 3 was tested in two selective reactions: photooxidation of phenol to hydroquinone and aerobic photooxidative condensation of benzylamine to N-benzylidenebenzylamine.}