Porous Nonlinear-Optical Material Based on a Twin-Nest-Shaped Heterothiometallic Cluster: {[NH 4 ][W 2 O 2 S 6 Cu 6 I 3 (4,4′-bipy) 4 ]‚5H 2 O} n Kexuan Huang, ² Yinglin Song, ‡ Zhaorui Pan, ² Yizhi Li, ² Xin Zhuo, ² and Hegen Zheng* ,²,§ State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing UniVersity, Nanjing 210093, People’s Republic of China, Department of Physics, Suzhou UniVersity, Suzhou 215000, China, and State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, People’s Republic of China Received April 26, 2007 A novel 3D porous coordination complex based on a twin-nest- shaped heterothiometallic cluster has been synthesized and characterized. The complex shows an unprecedented structure type and interesting nonlinear-optical properties. Its gas sorption property was studied and shown to be comparable to that of previously reported metal-organic frameworks. In recent years, porous coordination polymers have received much attention for their potential use in gas storage, 1 catalysis, 2 and other properties such as magnetism 3 and optical features. 4 Further functionalization of porous archi- tectures remains challenging, 5 and generally there are at least two synthetic strategies. One is the incorporation of a secondary functional group such as OH, 6 NH 2 , 7 COOH, 8 and pyridine 9 into the organic linkers to afford secondary binding sites for guest recognition or catalysis. Another is to use metal clusters as building blocks instead of single metal ions in the construction of porous networks. So far, several pre- formed metal clusters have been incorporated into infinite frameworks to afford materials with fascinating properties, including octahedral zinc carboxylate clusters, 10 metal- metal-bonded dimeric clusters, 11 [W 6 (µ 3 -S) 8 (CN) 6 ], 6-12 and hexarhenium chalcogenide clusters. 13 Mo(W)/Cu(Ag)/S heterothiometallic clusters have long been explored for their potential applications in catalysis and biological processes. 14 Our group in the past decade has systematically studied their nonlinear-optical (NLO) proper- ties. 15 Results from previous studies suggest improvements of NLO properties including the optical-limiting effect when converting monomeric thiometallic clusters into cluster- organic polymers. 16 In addition, the coordination modes of * To whom correspondence should be addressed. E-mail: zhenghg@ nju.edu.cn. 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