Tuning the Dimensionality of Inorganic Connectivity in Barium Coordination Polymers via Biphenyl Carboxylic Acid Ligands

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• 作者：Maw Lin Foo ; Satoshi Horike ; Jingui Duan ; Wenqian Chen ; Susumu Kitagawa
• 刊名：Crystal Growth & Design
• 出版年：2013
• 出版时间：July 3, 2013
• 年：2013
• 卷：13
• 期：7
• 页码：2965-2972
• 全文大小：458K
• 年卷期：v.13,no.7(July 3, 2013)
• ISSN：1528-7505

文摘

The synthesis and characterization of three barium coordination polymers with one-, two-, and three-dimensional (1-D, 2-D, 3-D) inorganic connectivity based on biphenyl carboxylic acid ligands are described. Employing biphenyl-3,3鈥?5,5鈥?tetracarboxylic acid (H₄BTTC) as a ligand, [Ba₂(BTTC)(H₂O)₂]_n (1, space group = Pn2₁a, a = 7.059(1) 脜, b = 12.432(2) 脜, c = 19.090(3) 脜), a coordination polymer with 1-D inorganic connectivity (I¹O²), can be synthesized. The coordinated water is strongly coordinated and removed at 270 掳C. By using 4,4鈥?biphenyldicarboxylic acid (H₂BPDC), [Ba(BPDC)]_n (2, space group = C2/m, a = 6.955(2) 脜, b = 5.947(1) 脜, c = 13.852 (4) 脜, 尾 = 92.399(4)掳) a coordination polymer with 2-D inorganic connectivity (I²O¹) is obtained. The connection of the Ba鈥揙 bonds in each layer is topologically similar to CaF₂. Using biphenyl-3,5,5鈥?tricarboxylic acid (H₃BPTC) as a ligand, [Ba₃(BPTC)₂(NMF)₅2NMF]_n (3, space group = I4̅2d, a = 25.984(3) 脜, c = 13.999(2) 脜) (NMF = N-methyl formamide), a structurally porous coordination polymer with rare 3-D inorganic connectivity (I³O⁰) can be synthesized. Hence, barium as a metal is extremely malleable with respect to construction of coordination polymers of different inorganic dimensionalities. 2 with I²O¹ connectivity demonstrates extraordinary thermal stability and maintains its crystallinity until decomposition at 590 掳C. The luminescence behavior of 1, 2, and 3 at room temperature has been investigated and is predominantly intraligand based.