0-D and 1-D inorganic-organic composite polyoxotungstates constructed from in-situ generated monocopper{sup II}-substituted Keggin polyoxoanions and copper{sup II}-organoamine complexes
- State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter and Graduate School of the Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)
Combination of in-situ generated monocopper{sup II}-substituted Keggin polyoxoanions with copper{sup II}-organoamine complexes under hydrothermal conditions results in seven inorganic-organic composite polyoxotungstates [Cu(en){sub 2}(H{sub 2}O)]{sub 2}{l_brace}[Cu(en){sub 2}][{alpha}-PCuW{sub 11}O{sub 39}Cl]{r_brace}.3H{sub 2}O (1), {l_brace}[Cu(en){sub 2}(H{sub 2}O)][Cu(en){sub 2}]{sub 2}[{alpha}-PCuW{sub 11}O{sub 39}Cl]{r_brace}.6H{sub 2}O (2), {l_brace}[Cu(en){sub 2}(H{sub 2}O)]{sub 2}[Cu(en){sub 2}][{alpha}-XCuW{sub 11}O{sub 39}]{r_brace}.5H{sub 2}O (3/4, X=Si{sup IV}/Ge{sup IV}), {l_brace}[Cu(deta)(H{sub 2}O){sub 2}]{sub 2}[Cu(deta)(H{sub 2}O)][{alpha}-XCuW{sub 11}O{sub 39}]{r_brace}.5H{sub 2}O (5/6, X=Ge{sup IV}/Si{sup IV}) and [Cu(dap){sub 2}]{sub 2}{l_brace}[Cu(dap){sub 2}]{sub 2}[Cu(dap){sub 2}][{alpha}-PCuW{sub 11}O{sub 39}]{sub 2}{r_brace} (7) (en=ethylenediamine, dap=1,2-diaminopropane and deta=diethylenetriamine). 1 is an isolated structure whereas 2 is a 1-D chain structure, but both contain [{alpha}-PCuW{sub 11}O{sub 39}Cl]{sup 6-} polyoxoanions. 3-6 contain the 1-D linear chains made up of [{alpha}-XCuW{sub 11}O{sub 39}]{sup 6-} polyoxoanions in the pattern of -A-A-A- (A=[{alpha}-XCuW{sub 11}O{sub 39}]{sup 6-}), while 7 demonstrates the first 1-D zigzag chain constructed from [{alpha}-PCuW{sub 11}O{sub 39}]{sub 2}{sup 10-} polyoxoanions via [Cu(en){sub 2}]{sup 2+} bridges in the pattern of -A-B-A-B- (A=[{alpha}-PCuW{sub 11}O{sub 39}]{sub 2}{sup 10-}, B=[Cu(en){sub 2}]{sup 2+}). The successful syntheses of 1-7 can provide some experimental evidences that di-/tri-/hexa-vacant polyoxoanions can be transformed into mono-vacant Keggin polyoxoanions under hydrothermal conditions. - Graphical abstract: A family of inorganic-organic composite polyoxotugstates have been harvested by combination of in-situ generated monocopper{sup II}-substituted Keggin polyoxoanions and copper{sup II}-organoamine complexes based on di-/tri-/hexa-vacant polyoxoanion precursors, CuCl{sub 2}.2H{sub 2}O and organoamines under hydrothermal conditions and structurally characterized by the elemental analysis, IR spectroscopy, TGA and single-crystal X-ray crystallography.
- OSTI ID:
- 21128433
- Journal Information:
- Journal of Solid State Chemistry, Vol. 181, Issue 9; Other Information: DOI: 10.1016/j.jssc.2008.04.042; PII: S0022-4596(08)00216-8; Copyright (c) 2008 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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