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  • Title: [W6S8] octahedral tungsten clusters functionalized with thiophene derivatives: toward polymerizable building blocks.
    Author: Perruchas S, Flores S, Jousselme B, Lobkovsky E, Abruña H, Disalvo FJ.
    Journal: Inorg Chem; 2007 Oct 15; 46(21):8976-87. PubMed ID: 17883265.
    Abstract:
    The functionalization of octahedral [W(6)S(8)] clusters with a family of phosphino-thiophene ligands has been investigated with the goal of synthesizing extended networks of [W(6)S(8)] units covalently linked to one another through thiophene-conjugated bridges. In addition to new phosphino-thiophene ligands, eight clusters were synthesized and characterized by (1)H and (31)P NMR spectroscopies, elemental analysis, and UV-vis absorption. These clusters are formulated [W(6)S(8)(T-PPh(2))6] (1a), [W(6)S(8)(T-PEt(2))(6)] (1b), [W(6)S(8)(2T-PPh(2))(6)] (2a), [W(6)S(8)(2T-PEt(2))(6)] (2b), [W(6)S(8)(3T-PPh(2))(6)] (3a), [W(6)S(8)(3T-PEt(2))(6)] (3b), [W(6)S(8)((2T)(3)P)(6)] (4), and [W(6)S(8)(2EDOT-PEt(2))(6)] (5) (T = thiophene and EDOT = 3,4-ethylenedioxythiophene). The molecular structure of six of them has been obtained by single-crystal X-ray diffraction analysis. All of them crystallize in the P1 triclinic space group except 3b, which has the P2(1)/c monoclinic symmetry. The redox behavior of both the ligands and the corresponding functionalized clusters has been investigated by cyclic voltammetry. An attempt to electropolymerize these species is also reported.
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