Molybdenum Carbonyl Complexes with a Polymerizable Phosphorus/Nitrogen/Phosphorus Ligand and Corresponding Conducting Metallopolymers

The design, synthesis, and characterization of the novel polymerizable ligand 3,5‐bis(3,4‐ethylenedioxythien‐2‐yl)‐N,N‐bis(2‐diphenylphosphinoethyl)‐phenylamine is achieved. The corresponding molybdenum complexes (EDOT)2PNP‐Mo(CO) n where n = 3,4 with carbonyls as ancillary ligands are also synthesized, and characterized by 1H NMR, 31P{1H} NMR, HRMS, FTIR (both the solution state spectrum between KBr discs and the solid‐state spectrum with attenuated total reflectance [ATR] apparatus). Single crystal X‐ray analysis of (EDOT)2PNP‐Mo(CO)3 complex is performed. The monomer complexes and the free ligand are electropolymerized to obtain the corresponding polymers that are studied electrochemically. The Mo/P and Mo/S ratios as well as the metal oxidations in the conducting metallopolymers are analyzed by X‐ray photoelectron spectroscopy. A novel electropolymerizable tridentate ligand (EDOT)2PNP is designed, synthesized, and characterized. Subsequently, two different molybdenum carbonyls are coordinated to the ligand. Molybdenum complexes with and without a direct communication with the conjugated polymer backbone are obtained. Both the free ligand and the complexes are electropolymerized and found to be electroactive. Metal oxidations on the polymers are analyzed by X‐ray photoelectron spectroscopy.