[W6S8] octahedral tungsten clusters functionalized with thiophene derivatives: toward polymerizable building blocks.
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.
Perruchas
Sandrine
S
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, USA. sandrine.perruchas@polytechnique.edu
Flores
Samuel
S
Jousselme
Bruno
B
Lobkovsky
Emil
E
Abruña
Hector
H
Disalvo
Francis J
FJ