Pd‐mediated polymerization of diazoacetates with aromatic ester group: Synthesis and photophysical property of poly(1‐pyrenylmethoxycarbonylmethylene)

Abstract

Pd‐mediated polymerization of 1‐pyrenylmethyl diazoacetates affords poly(1‐pyrenylmethoxycarbonylmethylene) (poly4′), whose CC main chain is tightly surrounded by pyrene groups. The intensity ratio of excimer emission to monomer emission (IE/IM) of poly4′ was more than 20 times higher than that of its vinyl polymer counterpart of poly(1‐pyrenylmethyl methacrylate) (polyPyrMA), clearly demonstrating much higher efficiency for excimer formation in poly4′, because of the tight arrangement of the pyrene groups around the main chain.

Hybrid Fluorescent Poly(silsesquioxanes) with Amide- and Triazole-Containing Side Groups for Light Harvesting and Cation Sensing

“…One of the possible resolutions is preparation of Py labeled polymer materials. Various types of optically active polymers have been prepared to date—e.g., Py functionalized polyacetylenes [ 21 ], poly(N-vinyl-2-pyrrolidone) [ 22 ], copolymers prepared though radical polymerization of n-butyl methacrylate and Py coupled methacrylates [ 23 ], poly(1-pyrenylmethoxycarbonylmethylene) [ 24 ], poly(methoxy diethylene glycol methacrylate) [ 25 ] and polystyrene [ 26 ]. Additionally, Py containing silicon-based materials have been prepared recently.…”

Pd‐initiated polymerization of diazo compounds bearing dialkoxyphosphinyl group and hydrolysis of the resulting polymers and oligomers to afford phosphonic acid‐containing products

“…Interesting to note is that the Rh‐diene initiated polymerization by Hetterscheid et al proceeds in a highly stereoselective manner, affording high molecular weight stereospecific polymers from alkyl diazoacetates . Although the polymers obtained by our Pd‐based initiators are basically atactic, monomers with a variety of ester substituents can be polymerized by the initiators . These results demonstrate the potential of the transition metal‐initiated polymerization of diazoacetates as a highly versatile method for the CC main chain polymer synthesis.…”

Polymerization of Alkyl Diazoacetates Initiated with Pd Complexes

“…Introduction of polar substituents into the polymethylene backbone has been achieved by the metal‐initiated oligomerization of alkyl diazoacetates, independently reported by Liu et al and our group . Preparation of high molecular weight poly(alkoxycarbonylmethylene)s from diazoacetates has been realized by de Bruin et al and our group, by using Rh‐diene complexes and Pd‐based initiating systems, respectively. Herein, the detail of the Pd‐initiated polymerization of a variety of diazoacetates will be described.…”