Synthesis and Photophysical Characterization of Group Transfer Polymers with Pendent Aryl Chromophores

Abstract

Naphthalene- and pyrene-labeled polymers (poly-3−5) prepared by group transfer polymerization of methyl 2-(2-naphthyl)acrylate, methyl 2-(1-pyrenyl)acrylate, and ethyl 5-(2-naphthyl)pentadienoate and ethyl 5-(2-naphthyl)hexadienoate, respectively, were studied as probes for backbone conformational rigidity. Excimer formation was observed in the steady-state fluorescence spectra, and the observation of biexponential decay of time-resolved fluorescence indicates two distinct environments for excimer formation. These, in turn, point to substantial conformational flexibility in the polymer backbone.

Anionic alternating copolymerization of α-arylacrylates with methyl methacrylate: Effect of monomer sequence on fluorescence

“…). Oligo(Fl2) exhibited strong emission of the excimer of fluorene moieties around 381 nm: Similar fluorescent properties were reported for poly(α‐arylacrylate)s . In contrast, poly(Fl2‐ co ‐MMA) exhibited weak excimer emission, whereas significant monomer emission at 318 nm was observed, the value of which is close to that of fluorene (312 nm).…”

“…Polymerizations of Py1 in toluene at 0 °C (Scheme , Table , Run 1) and 30 °C (Run 2) were initiated with Li‐ i PrIB, while copolymerization with MMA was carried out at 30 °C (Run 3). However, in any case no polymeric products were obtained, although GTP of Py1 was reported . Since the reaction mixtures colored yellow (See Supporting Information Fig.…”

“…It is known that fluorescent spectra of poly(vinylarene)s exhibit strong emission from excimers between the pendant aryl groups . For example, Fox et al reported the excimer emission of poly[α‐(1‐pyrenyl)acrylate] (poly‐ Py1 ) . However, there are some reports on the fluorescence property of an alternating copolymer of MMA and styrene, where the intramolecular excimer formation between the neighboring styrene units is almost completely suppressed, probably because the MMA units functioned as spacers to prevent the interaction of phenyl groups .…”

“…19 For example, Fox et al reported the excimer emission of poly[a-(1-pyrenyl)acrylate] (poly-Py1). 20 However, there are some reports on the fluorescence property of an alternating copolymer of MMA and styrene, where the intramolecular excimer formation between the neighboring Additional Supporting Information may be found in the online version of this article. styrene units is almost completely suppressed, probably because the MMA units functioned as spacers to prevent the interaction of phenyl groups.…”

Novel fluorescent amphiphilic block copolymers: photophysics behavior and interactions with DNA

“…The special structure makes higher fluorescence efficiency and reflects the red shift in excimer emssion. A similar phenonmenon was observed in other conjugated polymers [23].…”