Aggregation-Induced Emission Poly(meth)acrylates for Photopatterning via Wavelength-Dependent Visible-Light-Regulated Controlled Radical Polymerization in Batch and Flow Conditions

Abstract

A robust wavelength-dependent visible-light-regulated reversible-deactivation radical polymerization protocol is first reported for the batch preparation of >20 aggregation-induced emission (AIE)active polyacrylates and polymethacrylates. The resulting polymers possess narrow molar mass distributions (Đ ≈ 1.09−1.25) and high end-group fidelity at high monomer conversions (mostly >95%). This demonstrated control provides facile access to the in situ generation of complex sequence-defined tetrablock copolymers in one reactor, even while chain extending from less reactive monomers. Polymerizations can be successfully carried out under various irradiation conditions, including using UV, blue, green, and red LED light with more disperse polymers obtained at the longer, less energetic, wavelengths. We observe a red shift and wavelength dependence for the most efficient polymerization using LED illumination in a polymerization reaction. We find that the absorption of the copper(II) complex is not a reliable guide to reaction conditions. Moreover, the reported protocol is readily translated to a flow setup. The prepared AIE-active polymers are demonstrated to exhibit good photopatterning, making them promising materials for applications in advanced optoelectronic devices.

Highly differentiated multi-stimuli-responsive fluorescence performance of tetraphenylethylene-containing styrene–maleic acid copolymers induced by macromolecular architecture control

“…has been proposed as a novel approach to enriching the structural diversity and achieving optimized sensing and signaling properties. [20][21][22][23][24][25][26][27][28] For instance, Ishiwari et al discovered that a four-armed-star-block copolymer based on TPE-appended poly (acrylic acid) with POEGA segments exhibits a better balance of Ca 2+ -sensing and protein-adsorption-resistance properties over copolymers with other topologies. 22 Besides, hyperbranched AIE-active polymers have displayed an improved sensing ability to explosives compared to their linear analogues.…”

Simultaneously recorded photochemical action plots reveal orthogonal reactivity

“…8 Indeed, other research teams have confirmed the strong red-shift of photochemical reactivity, including photo-induced reversible deactivation radical polymerization (RDRP). 9,10 The most notable example is a recent report from the group of Haddleton, showing quantitative conversions of CuBr 2 /Me 6 TREN mediated photopolymerization of methyl acrylates in spectral regions of near zero absorptivity. 10 In addition to unravelling the wavelength resolved reactivity of photochemical reactions, we have applied photochemical reactions to construct complex macromolecules, including single chain nanoparticles (SCNPs), [11][12][13][14] which represent a contemporary research field.…”

“…9,10 The most notable example is a recent report from the group of Haddleton, showing quantitative conversions of CuBr 2 /Me 6 TREN mediated photopolymerization of methyl acrylates in spectral regions of near zero absorptivity. 10 In addition to unravelling the wavelength resolved reactivity of photochemical reactions, we have applied photochemical reactions to construct complex macromolecules, including single chain nanoparticles (SCNPs), [11][12][13][14] which represent a contemporary research field. [15][16][17] SCNPs have been applied in catalysis [18][19][20][21][22][23] and sensors.…”

“…8 Indeed, other research teams have confirmed the strong red-shift of photochemical reactivity, including photo-induced reversible deactivation radical polymerization (RDRP). 9,10 The most notable example is a recent report from the group of Haddleton, showing quantitative conversions of CuBr 2 /Me 6 TREN mediated photopolymerization of methyl acrylates in spectral regions of near zero absorptivity. 10…”

“…9,10 The most notable example is a recent report from the group of Haddleton, showing quantitative conversions of CuBr 2 /Me 6 TREN mediated photopolymerization of methyl acrylates in spectral regions of near zero absorptivity. 10…”