TY - JOUR
T1 - Model Coordination Complexes for Designing Poly(terthiophene)/Rh(I) Hybrid Materials with Electrochemically Tunable Reactivities
AU - Higgins, Thomas B.
AU - Mirkin, Chad A
PY - 1998/1/1
Y1 - 1998/1/1
N2 - The synthesis and characterization of two chiral, redox-active Rh(I) bis(diphenylphosphinite) monomers, complexes 3 and 4, are reported. Complex 4, [(η2-1,2- bis(diphenylphosphinite),4-oxo-6-(3′-α-terthiophene)Rh(I)(η 4-C7H8)]BF4, can be electrochemically polymerized to form poly-4, and the η4-C7H8 ligand can be hydrogenated in THF to form the metal-containing polymer 17. Polymer 17 is proposed to consist of a poly(terthiophene) backbone with Rh(I) phenyl-bridged dimers acting as cross-linkers between neighboring polymer chains. This structural formulation for polymer 17 is based upon its electrochemistry and a comparison with the solution chemistry of monomer 4. Significantly, this study discusses the importance of balancing polymerization potential, metal oxidation potential, and polymer ligating properties in the design of high surface area, polymeric, redox-switchable hemilabile ligands.
AB - The synthesis and characterization of two chiral, redox-active Rh(I) bis(diphenylphosphinite) monomers, complexes 3 and 4, are reported. Complex 4, [(η2-1,2- bis(diphenylphosphinite),4-oxo-6-(3′-α-terthiophene)Rh(I)(η 4-C7H8)]BF4, can be electrochemically polymerized to form poly-4, and the η4-C7H8 ligand can be hydrogenated in THF to form the metal-containing polymer 17. Polymer 17 is proposed to consist of a poly(terthiophene) backbone with Rh(I) phenyl-bridged dimers acting as cross-linkers between neighboring polymer chains. This structural formulation for polymer 17 is based upon its electrochemistry and a comparison with the solution chemistry of monomer 4. Significantly, this study discusses the importance of balancing polymerization potential, metal oxidation potential, and polymer ligating properties in the design of high surface area, polymeric, redox-switchable hemilabile ligands.
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U2 - 10.1021/cm970765e
DO - 10.1021/cm970765e
M3 - Article
AN - SCOPUS:0001018713
SN - 0897-4756
VL - 10
SP - 1589
EP - 1595
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 6
ER -