Synthesis and characterization of a π‐conjugated hybrid of oligothiophene and porphyrin

Abstract

5-(3-Thienyl)-10,15,20-triethyl-21H,23H-porphine (H 2 (ttep)) was synthesized and characterized. Oxidative polymerization of H 2 (ttep) gave a novel oligomeric porphyrin linked at the 2,5-positions of the thienyl group. Electric conductivity of 4 Â 10 À1 S/cm after I 2 doping indicated that the oligomer had a p-conjugated structure with a delocalization of p electrons over the thienylene backbone. PM3 calculations revealed a low HOCO-LUCO gap, which was consistent with the relatively high electric conductivity. Regioregular (head-to-tail) structure was inferred from spectroscopic and calculational results. The pendant porphyrin groups formed a regular J-type array along the thienylene backbone, which was indicated by a significant red shift of the Soret band maximum. Figure 6. (a) UV-vis spectra of H 2 (ttep) (3.5 Â 10 À7 mol/L) (solid curve) and undoped 1 (3.5 Â 10 À7 mol unit/L) (dotted curve) in DMSO. Optical path length was 1 cm. (b) UV-vis spectrum for the electropolymerized film of 1 on an ITO electrode. [Color figure can be viewed in the online issue, which is available at www.interscience. wiley.com.] 5410 OYAIZU ET AL.

Investigation of macromolecule–metal complexes as cathode catalyst in polymer electrolyte membrane fuel cell system

“…Cobalt(5,10,15,20‐tetraethylporphyrin) (CoTEtP) and cobalt(5‐mono(3‐thienyl)‐10,15, 20‐triethylporphyrin) (CM3ThTEtP) were synthesized from pyrrole and the corresponding aldehyde derivatives such as propionaldehyde and/or 3‐thienylaldehyde, respectively, according to the method reported previously 37–41. Pyrrole and cobalt acetate tetrahydrate were obtained from Tokyo Kasei, Co.…”