AgI/VV Heterobimetallic Frameworks Generated from Novel-Type {Ag2(VO2F2)2(triazole)4} Secondary Building Blocks: A New Aspe
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- 作者：Ganna A. Senchyk ; Valeriy O. Bukhan鈥檏o ; Andrey B. Lysenko ; Harald Krautscheid ; Eduard B. Rusanov ; Alexandr N. Chernega ; Miroslaw Karbowiak ; Konstantin V. Domasevitch
- 刊名：Inorganic Chemistry
- 出版年：2012
- 出版时间：August 6, 2012
- 年：2012
- 卷：51
- 期：15
- 页码：8025-8033
- 全文大小：682K
- 年卷期：v.51,no.15(August 6, 2012)
- ISSN：1520-510X
文摘
A series of new silver(I)-containing MOFs [Ag2(tr2ad)2](ClO4)2 (1), [Ag2(VO2F2)2(tr2ad)2]路H2O (2), [Ag2(VO2F2)2(tr2eth)2(H2O)2] (3), and [Ag2(VO2F2)2(tr2cy)2]路4H2O (4) supported by 4-substituted bifunctional 1,2,4-triazole ligands (tr2ad = 1,3-bis(1,2,4-triazol-4-yl)adamantane, tr2eth = 1,2-bis(1,2,4-triazol-4-yl)ethane, tr2cy = trans-1,4-bis(1,2,4-triazol-4-yl)cyclohexane) were hydrothermally synthesized and structurally characterized. In these complexes, the triazole heterocycle as an N1,N2-bridge links either two adjacent Ag鈥揂g or Ag鈥揤 centers at short distances forming polynuclear clusters. The crystal structure of compound 1 is based on cationic {Ag2(tr)4}2+ fragments connected in a 2D rhombohedral grid network with (4,4) topology. The neighboring layers are tightly packed into a 3D array by means of argentophilic interactions (Ag路路路Ag 3.28 脜). Bridging between different metal atoms through the triazole groups assists formation of heterobimetallic AgI/VV secondary building blocks in a linear V鈥揂g鈥揂g鈥揤 sequence that is observed in complexes 2鈥?b>4. These unprecedented tetranuclear {Ag2(VO2F2)2(tr)4} units (the intermetal Ag鈥揂g and Ag鈥揤 distances are 4.24鈥?.36 and 3.74鈥?.81 脜, respectively), in which vanadium(V) oxofluoride units possess distorted trigonal bipyramidal environment {VO2F2N}炉, are incorporated into 1D ribbon (2) or 2D square nets (3, 4) using bitopic 渭4-triazole ligands. The valence bond calculation for vanadium atoms shows +V oxidation state in the corresponding compounds. Thermal stability and photoluminescence properties were studied for all reported coordination polymers.