ABSTRACT
Sustainable carbon dots based on cellulose, particularly carboxymethyl cellulose carbon dots (CMCCDs), were confined in an inorganic network resulting in CMCCDs@SiO2. This resulted in a material exhibiting long afterglow covering a time frame of several seconds also under air. Temperature-dependent emission spectra gave information on thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) while photocurrent experiments provided a deeper understanding of charge availability in the dark period, and therefore, its availability on the photocatalyst surface. The photo-ATRP initiator, ethyl α-bromophenylacetate (EBPA), quenched the emission from the millisecond to the nanosecond time frame indicating participation of the triplet state in photoinduced electron transfer (PET). Both free radical and controlled radical polymerization based on photo-ATRP protocol worked successfully. Metal-free photo-ATRP resulted in chain extendable macroinitiators based on a reductive mechanism with either MMA or in combination with styrene. Addition of 9â ppm Cu2+ resulted in Mw/Mn of 1.4 while an increase to 72â ppm improved uniformity of the polymers; that is Mw/Mn=1.03. Complementary experiments with kerria laca carbon dots confined materials, namely KCDs@SiO2, provided similar results. Deposition of Cu2+ (9â ppm) on the photocatalyst surface explains better uniformity of the polymers formed in the ATRP protocol.
ABSTRACT
Sustainable carbon dots (CDs) based on furfuraldehyde (F-CD) resulted in a photosensitive material after pursuing the Alder-Longo reaction. The porphyrin moiety formed connects the F-CDs in a covalent organic network. This heterogeneous material (P-CD) was characterized by XPS indicating incorporation of the respective C, N and O moieties. Time resolved fluorescence including global analysis showed contribution of three linked components to the overall dynamics of the excited state. Electrochemical and photonic properties of this heterogeneous material facilitated photopolymerization in a photo-ATRP setup where either CuBr2 /TPMA, FeBr3 /Br- or a metal free reaction setup activated controlled polymerization. Chain extension experiments worked in all three cases showing end group fidelity for activation of controlled block copolymerization using MMA and styrene as monomers. Traditional radical polymerization using a diaryl iodonium salt as co-initiator failed.
ABSTRACT
NIR exposure at 790â nm activated photopolymerization of monomers comprising UV-absorbing moieties by using [CuII /(TPMA)]Br2 (TPMA=tris(2-pyridylmethyl)amine) in the ppm range and an alkyl bromide as initiator. Some of them comprised structural elements selected either from those showing proton transfer or photocycloaddition upon UV excitation. Polymers obtained comprise living end groups serving as macroinitiator for controlled synthesis of block copolymers with relatively narrow molecular weight distributions. Chromatographic results indicated formation of block copolymers produced by this synthetic approach. Free-radical polymerization of monomers pursued for comparison exhibited the expected broader dispersity of molecular weight compared to photo-ATRP. Polymerization of these monomers by UV photo-ATRP failed on the contrary to NIR photo-ATRP demonstrating the UV-filter function of the monomers. This work conclusively provides a new approach for the polymerization of monomers comprising UV-absorbing moieties through photo-ATRP in the NIR region. This occurred in a simple and efficient pathway. However, studies also showed that not all monomers chosen successfully proceeded in the NIR photo-ATRP protocol.
