Photosensitivity of Functional Polystyrene and Poly(methyl methacrylate) Synthesized by Controlled Radical Polymerization

Abstract

We report the synthesis and photosensitizing properties of various polystyrene and poly-(methyl methacrylate) that contain metal complex cores. The polymers were synthesized by atom transfer radical polymerization (ATRP) using metalloinitiators based on rhenium and ruthenium diimine complexes. The detailed structures of the initiators were determined by X-ray crystallography. In ATRP, the catalyst systems were composed of copper(I) bromide and 1,1,4,7,7-pentamethyldiethylenetriamine. The rates of polymerization depended on several factors such as the amounts of initiator, copper bromide, and ligand with respect to the monomer concentration. From the kinetic plots, the polymerizations showed first-order kinetics with respect to the monomer concentration, and the typical rate of polymerization is on the order of 10 -5 s -1 . The photoconducting properties of the polymers were studied using argon-ion laser (488 nm) as the light source. The metal complex cores may serve as efficient photosensitizers in the visible region, and the photoconductivities of the polymers are on the order of 10 -10 Ω -1 cm -1 . The experimental quantum yields were fitted into Onsager's equation, from which the primary yield and thermalization distance were calculated to be 0.02 and 1.3 to 1.8 nm, respectively.

Water‐Soluble, Disulfonated alpha‐Diimine Rhodium(I) Complexes: Synthesis, Characterisation and Application as Catalyst Precursors in the Hydroformylation of 1‐Octene

“…All reagents were purchased from Merck and used without further purification. 1,2‐bis(4‐hydroxylphenylimino) glyoxal, L1 and L2 were synthesised according to modified, previously reported methods. Nuclear Magnetic Resonance (NMR) spectra were recorded on either a Bruker Ultrashield 400 Plus ( 1 H: 400.22 MHz; 13 C: 100.65 MHz) or a Bruker 300 MHz ( 1 H: 300.08 MHz; 13 C: 75.46 MHz) spectrometer at ambient temperature.…”

Discussion Addendum for:Efficient Synthesis of Halomethyl‐2,2'‐Bipyridines: 4,4'‐Bis(Chloromethyl)‐2,2'‐Bipyridine

“…Bipyridyl units appear frequently in functionalized polymeric materials as ligands for metal atoms or to modify electronic or optical properties. [10][11][12][13][14] The bis(halomethyl)-bipyridine complexes and their corresponding compounds with ruthenium or iron were utilized as initiators to generate metallopolymers, including block polymers. [15][16][17][18][19][20][21] 1.…”

Light-Associated Reactions of Synthetic Polymers

“…125 The aryl alkyl borates that are paired with cationic chromophores can act as co-initiators in either UV or in visible light systems. [128][129][130][131][132] The mechanism of radical chain initiation by triphenylbutylborate salts involves photoinduced electron transfer from the borate anion to a chromophore in the excited state and probably formation of a triphenylbutylborate radical. [128][129][130][131][132] The mechanism of radical chain initiation by triphenylbutylborate salts involves photoinduced electron transfer from the borate anion to a chromophore in the excited state and probably formation of a triphenylbutylborate radical.…”

“…129 Chan and coworkers 130 or M = When the polymers are doped with a hole transporting triphenylamine, an enhancement in photoconductivity in the visible region is observed. The decay of the photoconductivity is nonexponential and responsive ion-conductive materials.…”