Fullerene Substitution of Donor/Acceptor Branched Disubstituted Polyacetylenes: Significantly Accelerated Polymerization by the C₆₀ Pendant

Abstract

A novel type of soluble donor/acceptor branched disubstituted polyacetylene (PA–C60) bearing C60 and soft pentyl moieties in side‐chains was synthesized successfully. The product has been characterized by FTIR, 1H NMR, 13C NMR, CH COSY, UV‐vis, and fluorescence spectroscopies, confirming its branched polymeric structure comprising polyacetylene chains and covalently bound C60 cages in side‐chains. Surprisingly, completely different from the conventional metathesis polymerization of acetylenes, it is found for the first time that the disubstituted monomer 4 can be polymerized within a very short reaction time (up to 1.5 min) and the molecular weight of the synthesized PA–C60 is independent of the reaction time. A plausible interpretation is proposed to understand the rapid polymerization reaction accelerated by the C60 pendant. The optical properties of PA–C60 were studied by UV‐vis absorption and fluorescence spectroscopies, which indicated that the fluorescence of PA–C60 is significantly enhanced compared to monomer 4, presumably due to its branched structure. SEM studies on the thin film morphology of PA–C60 in comparison with monomer 4 suggested the successful polymerization of monomer 4 and revealed that PA–C60 has a much smoother morphology than the aggregated morphology of monomer 4.magnified image

Fullerene‐Based Conducting Polymers: n‐Dopable Materials for Charge Storage Application

“…An exemplary procedure for synthesizing this polymeric material is shown in Scheme 18 . [ 167 ] First, the monosubstituted acetylenic monomer was synthesized from the commercially available okt‐2yn‐1‐ol and then reacted with fullerene C 60 and sarcosine in a Prato reaction to produce the C 60 ‐substituted monomer 32 . Monomer 32 was then subjected to the polymerization reaction with the catalyst WCl 6 ‐Ph 4 Sn or MoCl 5 ‐Ph 4 Sn, resulting in the formation of the poly‐ 32 polymer.…”