0-D and 1-D inorganic-organic composite polyoxotungstates constructed from in-situ generated monocopper(II)-substituted Keggin polyoxoanions and copper(II)-organoamine complexes

摘要

Combination of in-situ generated monocopper(II)-substituted Keggin polyoxoanions with copper(II)-organoamine complexes under hydrothermal conditions results in seven inorganic-organic composite polyoxotungstates [Cu(en)(2)(H2O)](2){[Cu(en)(2)][alpha-PCuW11O39Cl]}center dot 3H(2)O (1), {[Cu(en)(2)(H2O)]}Cu(en)(2)](2) [alpha-PCuW11O39Cl]}center dot 6H(2)O (2), [Cu(en)(2)(H2O)](2)[Cu(en)(2)][alpha-XCuW11O39]}center dot 5H(2)O (3/4, X = Si-IV/Ge-IV), {[Cu(deta)(H2O)(2)](2)[Cu(deta)(H2O)][alpha-XCuW11O39]}center dot 5H(2)O (5/6, X = Ge-IV/Si-IV) and [Cu(dap)(2)](2){ [Cu(dap)(2)](2)[Cu(dap)(2)][alpha-PCuW11O39](2)} (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-PCuW11O39Cl](6-) polyoxoanions. 3-6 contain the 1-D linear chains made up of [alpha-XCuW11O39](6-) polyoxoanions in the pattern of -A-A-A- (A = [alpha-XCuW11O39](6-)), while 7 demonstrates the first 1-D zigzag chain constructed from [alpha-PCuW11O39](2)(10-) polyoxoanions via [Cu(en)(2)](2+) bridges in the pattern of -A-B-A-B- (A = [alpha-PCuW11O39](2)(10-), B = [Cu(en)(2))](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. (C) 2008 Elsevier Inc. All rights reserved.