3-D Silver(I)鈥擫anthanide(III) Heterometallic-Organic Frameworks Constructed from 2,2鈥?Bipyridine-3,3鈥?dicarboxylic Acid: Synthesis, Structure, Photoluminescence, and Their Remarkable Thermostability

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• 作者：Yunshan Zhou ; Xiaomin Li ; Lijuan Zhang ; Yan Guo ; Zonghai Shi
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：April 7, 2014
• 年：2014
• 卷：53
• 期：7
• 页码：3362-3370
• 全文大小：428K
• 年卷期：v.53,no.7(April 7, 2014)
• ISSN：1520-510X

文摘

A new family of silver(I)鈥搇anthanide(III) heterometallic-organic frameworks having the formula [AgLn(bpdc)₂] (Ln = Eu (1), Tb (2), Sm (3), Dy (4), Y (5), Yb (6), Er (7), Ho (8); H₂bpdc = 2,2鈥?bipyridine-3,3鈥?dicarboxylic acid), each of which crystallizes in the monoclinic space group C2/c with Z = 4, has been hydrothermally synthesized. The compounds were characterized by means of IR, elemental analysis, thermogravimetric-differential thermal analysis, and powder X-ray diffraction (XRD), wherein compounds 1, 2, and 4鈥?b>8 were structurally characterized. The powder XRD and single-crystal structures of the title compounds indicate that all the compounds are isostructural and feature a three-dimensional (3-D) open framework. In the structures of the compounds, bpdc^{2鈥?/sup> ligands link Ln3+ through their carboxylic groups, resulting in the formation of a one-dimensional {Ln(bpdc)₂}_n infinite chain along the c direction. The adjacent chains are then connected to each other through the coordination interaction between Ag+ and the pyridyl N atoms of bpdc2鈥?/sup> ligands from the chains, resulting in a 3-D (2,4,6)-connected open framework with (411路64)(43路82路10)(8)₂ topology. The compounds show remarkable good thermally stability up to 370 掳C because neither aquo ligands nor lattice water molecules exist in the composition of the compounds. The photoluminescent properties of compounds 1 and 2 were studied in detail. The energy level of the triplet states of the ligand H₂bpdc 21鈥?05 cm鈥? (465 nm) was determined based on the 77 K emission spectrum of the compound [Gd₂(bpdc)₃(phen)₂(H₂O)₂]路6H₂O 9. The 5D₀ and 5D₄ emission lifetimes (1.58 and 1.76 ms) and the overall quantum yields (21% and 22%) were determined for the compounds 1 and 2, respectively.}