Vinyl monomers bearing chromophore moieties and their polymers. XI. Synthesis and photochemical behavior of carbazole‐containing methacrylic monomers and their polymers

Abstract

Three carbazole‐containing methacrylic monomers, 2‐(N‐carbazolyl)ethyl methacrylate(CzEMA), 6‐(N‐carbazolyl)hexyl methacrylate(CzHMA), and 11‐(N‐carbazolyl)undecyl methacrylate (CzUMA), and their saturated model compounds, 2‐(N‐carbazolyl)ethyl isobutyrate, 6‐(N‐carbazolyl)hexyl isobutyrate, and 11‐(N‐carbazolyl)undecyl isobutyrate, were synthesized and polymerized. UV absorption spectra showed that there was either negligible or no interaction between the carbon–carbon double bond of the methacrylic group and the carbazolyl chromophore moiety in the ground state for these monomers. Fluorescence spectra of the monomers, their model compounds, and the polymers were recorded in the solvents with different polarities. CzEMA exhibited the fluorescence structural self‐quenching effect (SSQE), but CzHMA and CzUMA did not. In addition, the SSQE of CzEMA depended strongly on the polarity of the solvents. That is, the stronger the polarity of a solvent was, the more obvious the SSQE was. Therefore, the SSQE of CzEMA mainly was caused by the intramolecular charge‐transfer interaction between the excited electron‐donating carbazolyl chromophore moiety and the electron‐accepting carbon–carbon double bond of the methacrylic group. This was confirmed by the fluorescence‐decay curves and the fluorescence lifetimes of the monomers, their model compounds, and the polymers. The monomers, their model compounds, and the polymers initiated the photopolymerization of methyl methacrylate (MMA) upon UV irradiation. CzEMA showed greater initiation ability than the other two monomers and their model compounds; this was ascribed to the photoinduced intramolecular charge‐transfer interaction. The higher initiation efficiency of the homopolymers compared to that of the copolymers with MMA was interpreted as the result of singlet energy migration of the excited carbazolyl chromophores along the polymer chains. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 679–688, 2000

Palladium-based micellar nanohybrids: preparation and nonlinear optical response

“…The synthesis of the monomer CbzEMA was performed in two steps by following a modied methodology reported in the literature. 31,36,37 A DMF solution of carbazole (19 g, 0.114 mol) and ethylene carbonate (11 g, 0.125 mol) was placed under reux for 8 h in the presence of KOH (1.9 g). Aer been cooled down to room temperature, the reaction mixture was ltered and then poured into a large amount of water (4 L).…”

Well-defined fluoro- and carbazole-containing diblock copolymers: synthesis, characterization and immobilization onto Au-coated silicon surfaces

“…The synthesis of 2-(N-carbazolyl)ethyl methacrylate was accomplished in two steps by following a modified methodology based on previous literature reports. 31,36,37 2-(N-Carbazolyl)ethanol was synthesized first and subsequently modified to generate 2-(N-carbazolyl) ethyl methacrylate. For the synthesis of 2-(N-carbazolyl)ethanol, carbazole (19.0 g, 0.114 mol) was reacted with ethylene carbonate (11.0 g, 0.125 mol) in DMF (200.0 mL) under reflux (110-130 uC) for 8 h in the presence of KOH (1.9 g, 0.034 mol).…”

Photosensitizers and Photoinitiators

“…102 Upon irradiation, the poly(carbazolylethyl methaclylate) are claimed to show greater initiation ability than similar low molecular weight model compounds. 102 Upon irradiation, the poly(carbazolylethyl methaclylate) are claimed to show greater initiation ability than similar low molecular weight model compounds.…”

“…102 Upon irradiation, the poly(carbazolylethyl methaclylate) are claimed to show greater initiation ability than similar low molecular weight model compounds. [102][103][104][105] The photoinitiating efficiency of silane polymers with thioxanthone side groups was found to depend not upon exiplex formation with tertiary amines but rather upon the micro heterogeneity of the distribution of the partners in the initiation process. Also, the initiation efficiency of the homopolymers is higher than that of copolymers with methyl methacrylate.…”