Intramolecular photoinduced rearrangements via electron-transfer-induced, concerted bond cleavage and cation radical/radical coupling

Saeva, F. D.; Breslin, David T.; Luss, Henry R.

doi:10.1021/ja00014a028

Cited by 62 publications

(42 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Marder and Saeva et al proved that the byproducts of PAG photodecomposition are the main precursor and free radical adducts . Our study on the excited state dynamics of a D‐π‐A type sulfonium‐based alkoxystilbene PAG also led to the same conclusions .…”

Section: Resultssupporting

confidence: 85%

“…), thereby decreasing the molar extinction coefficients of PI‐PAG but increasing the electron delocalization in the molecular structure; these changes caused the spectra redshift relative to its precursor. Saeva confirmed that the photoacid generation reaction of arylsulfonium salts may occur either by direct excitation of π– σ * (sulfur–carbon bond) transition or excitation of the π– π * transition, followed by intramolecular electron transfer to σ * on the sulfur–carbon bond . In both cases, subsequent homolytic cleavage of the S‐C bond leads to the formation of radical cation on the sulfur‐containing fragment and a neutral radical on the carbon fragment.…”

Section: Resultsmentioning

confidence: 86%

“…Precursor (197.7 mg, 0.4 mmol), Cs 2 CO 3 (274.3 mg, 0.8 mmol) was added to a 100‐mL flask along with 20.0 mL of dry dichloromethane and the mixture was stirred under −78 °C for 30 min. Then methyl trifluoromethanesulfonate (76.0 mg, 0.5 mmol) was syringed into the solution . After stirring at this temperature for 2 h, the mixture was warmed to room temperature and stirred for another 48 h. Then, column chromatography was used for separation and purification (dichloromethane: methanol 1: 5, v/v, 500 mL) to obtain yellow product (sulfomium trifluoromethanesulfonate).…”

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Dual roles for promoting monomers to polymers: A conjugated sulfonium salt photoacid generator as photoinitiator and photosensitizer in cationic photopolymerization

Jin

Malval

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

View full text Add to dashboard Cite

An efficient strategy for comprehensive utilization of the conjugated sulfonium salt photoacid generator (PAG), namely, 3‐{4‐[4‐(4‐N,N′‐diphenylamino)‐styryl]phenyl}phenyl dimethyl sulfonium hexafluoroantimonate, was developed through photoinitiated cationic photopolymerization (CP) of epoxides and vinyl ether upon exposure to near‐UV and visible light‐emitting diodes (LEDs; e.g., 365, 385, 405, and 425 nm). Photochemical mechanisms were investigated by UV–vis spectra, molecular orbital calculations, fluorescence, cyclic voltammetry, and electron spin resonance spin‐trapping analyses. Compared with commercial PAGs, the prepared conjugated sulfonium salt generated H+, which can be used as photoinitiator. Moreover, the fluorescent byproducts from photodecomposition can be used as photosensitizer of commercial iodonium salt in the photoinitiating systems of CP. These novel D‐π‐A type sulfonium‐based photoinitiating systems are efficient (epoxide conversion = 85–90% and vinyl conversion >90%; LEDs upon exposure to 365–425 nm) even in low‐concentration initiators (1%, w/w) and low curing light intensities (10–40 mW cm−2). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2722–2730

show abstract

Section: Resultssupporting

confidence: 85%

Section: Resultsmentioning

confidence: 86%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Dual roles for promoting monomers to polymers: A conjugated sulfonium salt photoacid generator as photoinitiator and photosensitizer in cationic photopolymerization

Jin

Malval

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

View full text Add to dashboard Cite

show abstract

“…28,36,50,51 All detailed synthetic procedures, characterization were shown in the ESI (Fig. PAGs were prepared by Saeva's methods.…”

Section: Synthesis Of Precursors and Pagsmentioning

confidence: 99%

One/two-photon-sensitive photoacid generators based on benzene oligomer-containing D–π–A-type aryl dialkylsulfonium salts

Jin

Xie

et al. 2015

RSC Adv.

View full text Add to dashboard Cite

Novel sulfonium-based D-p-A photoacid generators (PAGs) with a benzene oligomer (from one to four) as a p-conjugated system that are highly photosensitive in the near-ultraviolet region (365 nm) were prepared.The maximum absorption and molar extinction coefficients of the PAGs redshifted and enhanced with the increasing length of the conjugated systems. The quantum yields of PAGs were high (three of them were over 0.6) and improved by adjusting the number of the phenyl rings. The quantum chemical calculation results proved that the molecular configuration and nature of the frontier orbitals are crucial factors which affect PAG performance. Photopolymerization kinetic results demonstrated that these sulfoniumbased PAGs were highly efficient cationic photoinitiators, and the i-line sensitivities were evaluated based on the photolithographic performance of the PAG-containing SU-8 resins. In addition, the two-photon absorption cross sections (d 700 nm > 400 GM) matched the requirements needed in the 3D fabrication of polymer microstructures. † Electronic supplementary information (ESI) available: Details of the organic synthesis and characterization, photodecomposition, photoacid generation, TGA curves, photopolymerization, photolithography and two-photon absorption. See

show abstract

“…173,174 Performance of diaryl chloronium and diaryl bromonium salts was studied by Nickers and Abu. 179 It appears that the general behavior of these materials is similar to diphenyl iodonium and triphenyl sulfonium salts. 179 It appears that the general behavior of these materials is similar to diphenyl iodonium and triphenyl sulfonium salts.…”

Section: Photosensitizers and Photoinitiatorsmentioning

confidence: 96%

Photosensitizers and Photoinitiators

Ravve¹

Light-Associated Reactions of Synthetic Polymers

View full text Add to dashboard Cite

Intramolecular photoinduced rearrangements via electron-transfer-induced, concerted bond cleavage and cation radical/radical coupling

Cited by 62 publications

References 2 publications

Dual roles for promoting monomers to polymers: A conjugated sulfonium salt photoacid generator as photoinitiator and photosensitizer in cationic photopolymerization

Dual roles for promoting monomers to polymers: A conjugated sulfonium salt photoacid generator as photoinitiator and photosensitizer in cationic photopolymerization

One/two-photon-sensitive photoacid generators based on benzene oligomer-containing D–π–A-type aryl dialkylsulfonium salts

Photosensitizers and Photoinitiators

Contact Info

Product

Resources

About