Organic鈥揑norganic Hybrids Based on Monovacant Keggin-type Silicotungstates and 3d-4f Heterometals
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- 作者：Shaowei Zhang ; Junwei Zhao ; Pengtao Ma ; Huanni Chen ; Jingyang Niu ; Jingping Wang
- 刊名：Crystal Growth & Design
- 出版年：2012
- 出版时间：March 7, 2012
- 年：2012
- 卷：12
- 期：3
- 页码：1263-1272
- 全文大小：676K
- 年卷期：v.12,no.3(March 7, 2012)
- ISSN：1528-7505
文摘
A series of organic鈥搃norganic hybrid lacunary Keggin silicotungstate 3d-4f heterometallic derivatives, {[Cu (en)2]1.5Ln[(伪-SiW11O39)2]}220鈥?/sup> [Ln = GdIII for 1, TbIII for 2, DyIII for 3, ErIII for 4, LuIII for 5], {[Cu(en)2]1.5Ln[(伪-SiW11O39)]}2鈥?/sup> [Ln = LaIII for 6, CeIII, for 7] and {[Cu(en)2(H2O)][Cu(en)2]nLn[(伪-SiW11O39)2]}m鈭?/sup> [(Ln, n, m) = (PrIII, 2, 7) for 8, (SmIII, 3, 5) for 9] (en = ethylenediamine) have been successfully synthesized under hydrothermal conditions and further characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP-AES) analyses, X-ray powder diffraction (XRPD), IR spectra, thermogravimetric (TG) analyses, and single-crystal X-ray diffraction. The common features of 1鈥?b>5 and 8鈥?b>9 are that they all consist of a sandwich-type [Ln(伪-SiW11O39)2]13鈥?/sup> polyoxoanion, whereas both 6 and 7 consist of the unusual 1:1 [Ln(伪-SiW11O39)]5鈥?/sup> units and [Cu(en)2]2+ coordination cations. 1鈥?b>5 show dimeric structures, and 6鈥?b>9 display unprecedented three-dimensional (3D) frameworks, representing the first 3D 3d-4f heterometallic silicotungstates. The features of 6 and 7 are that the components are closely packed along the 21 screw axis to generate scarce 5-connected network structures with the Schl盲fli symbol of (48路62), while 8 and 9 exhibit the 4-connected (66) topology and 6-connected (48路54路63) topology structures, respectively. Furthermore, 2, 3, and 9 manifest apparent fluorescence signals, which can be assigned to the characteristic emissions of TbIII, DyIII, and SmIII cations, respectively.