Molecular and multidimensional polyoxotungstates functionalized by {Cu(bpy)}2+ groups | doi.page

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Molecular and multidimensional polyoxotungstates functionalized by {Cu(bpy)}2+ groups

Dalton Transactions2005Iss. 24, pp. 3913–3913

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Laurent Lisnard, Anne Dolbecq, Pierre Mialane, Jérôme Marrot, Épiphane Codjovi, F. Sécheresse

Abstract

Five new materials built from polyoxotungstates and Cu(ii) ions as linkers have been synthesized by hydrothermal reactions from a mixture of sodium tungstate, copper chloride and bipyridine. The value of the initial pH, the nature of the heteroelement (P or Si) and of the ligand (2,2'- and/or 4,4'-bipyridine) permit the control of the nature of the polyoxotungstate clusters and their connectivity via the copper ions, and hence the dimensionality of the framework. A single phase has been obtained with silicon as heteroelement at an initial pH of 5, namely the 2D material [SiW(12)O(40)][Cu(2,2'-bpy)(2)](2).10H(2)O (1) with saturated Keggin polyoxotungstates linked by {Cu(2,2'-bpy)(2)}(2+) groups. With phosphorous as heteroelement and at the same initial pH, three different structures have been isolated according to the nature of the ligand. Indeed, the two 1D materials [{Cu(5)(2,2'-bpy)(5)(H(2)O)(HPO(4))(PO(4))}PW(11)CuO(39)].6H(2)O (2) with 2,2'-bpy and [4,4'-Hbpy][{Cu(2)(2,2'-bpy)(2)(4,4'-bpy)(2.5)}PW(11)CuO(39)].16H(2)O (3) with a mixture of 2,2'- and 4,4'-bpy have been characterized, and a coordination polymer with polyoxometalate guests Na(3)[4,4'-Hbpy]{Cu(4)(4,4'-bpy)(8)(H(2)O)(8)}[PW(11)CuO(39)(H(2)O)][PW(10)Cu(2)O(38)(H(2)O)(2)].38H(2)O (4) with 4,4'-bpy has been obtained. Finally, in basic medium (pH = 10) the unprecedented molecular cluster Na(2)[{Cu(8)(2,2'-bpy)(8)}(PW(8)O(31))(2)].15H(2)O (5) has been evidenced. Magnetic studies of compound 2 revealed that the predominant interactions involve only 4 paramagnetic centers, which are interacting within pairs, among the 6 Cu(ii) centers. The chi(M)T=f(T) curve can be fitted using the dinuclear expression appropriate to the HDVV isotropic exchange Hamiltonian H=-JS(1)xS(2), with S(1)=S(2)=(1/2) and J=-105.4 cm(-1), showing strong antiferromagnetic interactions within the two Cu(ii) pairs.

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Abstract

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