Synthesis of a <i>meso</i>‐Tetraalkylporphycene Bearing Reactive Sites: Toward Porphycene–Polydimethylsiloxane Hybrids with Enhanced Photophysical Properties

Abstract

meso ‐Tetraalkyl porphycenes exhibit unique optical properties with wide potential applications. The very fact that incorporation of porphycenes into polymeric materials is rare, make this approach a particularly attractive one. In this work, meso ‐tetrakis(3‐butenyl)porphycene bearing four terminal olefin groups is prepared via two synthetic strategies: 1) the McMurry reaction using 5,5′‐diacyl‐2,2′‐bipyrroles as precursors and 2) the oxidative coupling of dipyrroethenes. The newly obtained porphycene has been characterized by single X‐ray crystallography. A porphycene–polydimethylsiloxane hybrid film is successfully prepared by a platinum‐catalyzed hydrosilylation reaction. The hybrid film can be anchored with tweezers, showing a weak red emission with a quantum yield of 0.4 % at room temperature, whose intensity drastically increases reaching a quantum yield of 6.7 % in liquid nitrogen (77 K). This report represents the first example of porphycene‐containing elastomeric films for potential application in various fields.