Synthesis of a meso‐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 crys- [a]

2 + 2 Can Make Nearly a Thousand! Comparison of Di- and Tetra-Meso-Alkyl-Substituted Porphycenes

“…Among these studies, particularly important in terms of possible applications are those devoted to spectral and photophysical properties. , Porphycenes are very promising as sensitizers in photodynamic therapy, the main, but not the only theme of numerous patents. Other areas of possible use of porphycenes based on interaction with light include photoelectrochemical devices, near-IR absorbing and emitting fluorophores, − preparation of new electrochromic, liquid crystalline, and elastomeric materials. However, comparative research on the photophysical properties of different porphycenes has been rather limited.…”

Rectangular Holes in Porphyrin Isomers Act As Mono- and Binucleating Ligands: Stereochemistry of Mono- and Diboron Porphycenes and Their Protonation Behaviors

“…Structurally, porphycenes consist of two 2,2′-bipyrrole subunits linked by two ethylene linkers resulting in a smaller and more rectangular N 4 cavity than porphyrin, which causes the porphycenes to exhibit a unique coordination site. In recent years, the exploration of new synthetic methods of porphycenes has received considerable attention due to the synthetic challenges in typical methods. − The lack of efficient and economical synthetic methods for large scale porphycene production inhibited the growth of coordination chemistry of porphycene compared to that of its parent isomer, porphyrin. − Indeed, homo- or heterobinuclear complexes of porphycenes are rare. , Against this background, we have recently succeeded in the large scale synthesis of porphycenes with a facile method . This progress encouraged us to investigate an extensive study of the coordination chemistry of porphycene.…”

Light-Activated Antibacterial Polymeric Surface Based on Porphycene

“…Ono et al recently reported the synthesis of a meso-tetraalkylporphycene bearing reactive sites and the formation of porphycene-polydimethylsiloxane hybrid films with remarkable photophysical properties. 34 Abe et al informed the oxidative electrochemical polymerization of an axially bound bithiophene-pyridine complex of ruthenium(III)porphycene and the formation of a polymeric film on indium tin oxide (ITO) electrodes. 35 This limited number of investigations of porphycenes in comparison with porphyrins 36 could be understood due to their complex, expensive, and ineffective synthetic sequences.…”

“…Even though that porphycenes possess the mentioned advantages over porphyrins, − , few works have been reported using compounds based on the porphycene structure for PDI. − Furthermore, there are even fewer studies focusing on incorporating these constitutional isomers into polymeric materials. Ono et al recently reported the synthesis of a meso -tetraalkylporphycene bearing reactive sites and the formation of porphycene-polydimethylsiloxane hybrid films with remarkable photophysical properties . Abe et al informed the oxidative electrochemical polymerization of an axially bound bithiophene-pyridine complex of ruthenium­(III)-porphycene and the formation of a polymeric film on indium tin oxide (ITO) electrodes .…”