Organosilane Photochemistry

Steinmetz, Mark G.

doi:10.1021/cr00037a017

Cited by 124 publications

(82 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Evaluation of the spectra shows that the absorption maxima of the silyl-substituted naphthalene derivatives 2-6 shift by 8-9 nm to longer wavelengths and their molecular absorption coefficients () increase, compared with those of naphthalene (1). Similarly, analysis of the fluorescence spectra of aerated cyclohexane solutions of these compounds ( Figure 3) demonstrates that silyl substitution causes emission maxima to shift to longer wavelengths by 4-5 nm and fluorescence intensities to increase, relative to those of naphthalene.…”

Section: Effects Of Hydrogen Atom and Alkyl Group Containing Substitumentioning

confidence: 99%

“…Absorption and fluorescence spectra of cyclohexane solutions of 1,4-bis(trimethylsilyl)naphthalene (7), 1,4-bis(dimethylsilyl)naphthalene (8), and 1,4-bis(tert-butyldimethylsilyl)naphthalene (9) were recorded in order to compare their photophysical properties with those of 1-(trimethylsilyl)naphthalene (2) and naphthalene (1) (Figures 4 and 5). Analysis of the spectra shows that, in general, the absorption maxima of 7-9 occur at longer wavelengths than those of 2 and that the spectrum of the di-tert-butyldimethylsilyl derivative 9 displays the most dramatic bathochromic shift.…”

Section: Absorption and Fluorescence Properties Of Mono-and Di-silyl mentioning

confidence: 99%

“…The photochemistry of organosilicon compounds [1] has OPEN ACCESS been investigated from the perspective of absorption and emission spectroscopic properties of polysilanes [2], the generation of silylenes and disilenes by photoirradiation to oligosilanes [3][4][5][6][7][8], the formation of intramolecular charge transfer complexes of aromatic disilanes [9,10], and photoinduced electron transfer reactions of organosilicon compounds [11][12][13][14]. In addition, the enhancing effects of silyl groups on the fluorescence intensities of aromatic hydrocarbons, such as anthracenes, naphthacenes, pentacenes, triphenylenes, and pyrenes, has been probed and discussed in detail earlier [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Absorption and Fluorescence Spectroscopic Properties of 1- and 1,4-Silyl-Substituted Naphthalene Derivatives

Maeda

Mizuno

2012

Molecules

View full text Add to dashboard Cite

Silyl-substituted naphthalene derivatives at the 1-and 1,4-positions were synthesized and their UV absorption, fluorescence spectroscopic properties, and fluorescence lifetimes were determined. Analysis of the results shows that the introduction of silyl groups at these positions of the naphthalene chromophore/fluorophore causes shifts of the absorption maxima to longer wavelengths and increases in fluorescence intensities. Bathochromic shifts of the absorption maxima and increases in fluorescence intensities are also promoted by the introduction of methoxy and cyano groups at the naphthalene 4-and 5-positions. In addition, the fluorescence of 9,10-dicyanoanthracene is efficiently quenched by these naphthalene derivatives with Stern-Volmer plot calculated rate constants that depend on the steric bulk of the silyl groups.

show abstract

Section: Effects Of Hydrogen Atom and Alkyl Group Containing Substitumentioning

confidence: 99%

Section: Absorption and Fluorescence Properties Of Mono-and Di-silyl mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Absorption and Fluorescence Spectroscopic Properties of 1- and 1,4-Silyl-Substituted Naphthalene Derivatives

Maeda

Mizuno

2012

Molecules

View full text Add to dashboard Cite

show abstract

“…14,15 The intermolecular reactions between highly unstable silenes and the compounds containing functional groups such as OH [16][17][18][19][20][21][22] , C=O…”

Section: 13mentioning

confidence: 99%

“…14, 15 The intermolecular reactions between highly unstable silenes and the compounds containing functional groups such as OH [16][17][18][19][20][21][22] , C=O [23][24][25][26] , and C=C 27-31 bonds resulted in the formation of the addition products.…”

Section: 13mentioning

confidence: 99%

Photoreactions of (2-Acetoxyphenyl)pentamethyldisilane

Park¹,

Kim²

2011

Bulletin of the Korean Chemical Society

View full text Add to dashboard Cite

It is well known that the photoreactions of aryldisilanes show four reaction patterns 1 since the first report on the photolysis of phenylpentamethyldisilane and (p-tolyl)pentamethyldisilane by Ishikawa et al.2 in 1975 : (path a) formation of a silene compound via elimination of a trimethylsilane 3 , (path b) formation of a silene compound arising from 1,3-shift of trimethylsilyl radical, which is formed via homolytic cleavage of silicon-silicon bond [4][5][6][7][8][9] , (path c) formation of a trimethylsilyl compound via elimination of a silylene 10,11 , (path d) formation of a direct solvolysis compound via elimination of a trimethylalkoxysilane or pentamethylalkoxydisilane. 12,13Silenes having the C=Si moiety are regarded as highly interesting intermediates. Consequently the synthesis and reactions of silenes as useful intermediates have been extensively investigated.14,15 The intermolecular reactions between highly unstable silenes and the compounds containing functional groups such as OH [16][17][18][19][20][21][22] , C=O 23-26, and C=C 27-31 bonds resulted in the formation of the addition products.In connections with the photolysis of aryldisilanes, we recently disclosed the intramolecular reactions between the silene intermediates resulted from the photoreactions of ortho-substituted aryldisilanes and ortho-substituents to give the novel silicon-containing heterocyclic compounds such as the photoinduced intramolecular reactions of (2-substitutedphenyl)pentamethyldisilanes 32 , (2-alkoxymethylphenyl)pentamethyldisilanes 33 , 2-(pentamethyldisilanyloxy)phenylpentamethyldisilane 34 and (2-hydroxyethoxyphenyl)pentamethyldisilane. 35 We have also investigated the synthesis of siliconcontaining heterocyclic compounds through the intramolecular reactions of silacyclopropene or 1-silaallene moiety with ortho-substituents in ortho-substituted-phenylethynylpentamethyldisilanes 36. As a part of our continuous studies utilizing the silenes as reaction intermediates for the synthesis of silicon-containing heterocyclic compounds, we investigated the photoreactions of (2-acetoxyphenyl)pentamethyldisilane which has the acetoxy group as ortho substituent to phenylpentamethyldisilane because it was expected that the novel photoproducts could be formed from the intramolecular reaction of ortho-substituted acetoxy group with the silene intermediate. In this note, we would like to report the detailed photochemical study of (2-acetoxyphenyl)pentamethyldisilane.The starting (2-acetoxyphenyl)pentamethyldisilane 2 was prepared from the reaction of (2-hydroxyphenyl)pentamethyldisilane 1 35 with acetyl chloride using triethylamine as base in tetrahydrofuran at room temperature (Scheme 1).In order to investigate a possibility that the C=O bond as ortho substituent in 2 reacts intramolecularly with a silene, the photolysis of 2 was performed.Irradiation of 2 in deaerated benzene with 254nm UV light afforded two photo-Fries rearrangement products 4 (18% yield) and 5 (10% yield) along with some decomposition products of unknown structu...

show abstract

Steric Effects of Silyl Groups

Hwu

Tsay

Cheng

2009

Patai's Chemistry of Functional Groups

View full text Add to dashboard Cite

Introduction An Order in Increasing Size of Silyl Groups Comparison of Organosilyl Groups in Substrates Comparison of the Influence Resulting from Hydrogen Atom and Alkyl Groups versus Silyl Groups Reactivity of Silicon‐Containing Reagents Solvolysis of Various Organosilanes Change of Physical, Chemical and Spectroscopic Properties by Introduction of Silyl Groups Conclusion Acknowledgment

show abstract

Organosilane Photochemistry

Cited by 124 publications

References 0 publications

Absorption and Fluorescence Spectroscopic Properties of 1- and 1,4-Silyl-Substituted Naphthalene Derivatives

Absorption and Fluorescence Spectroscopic Properties of 1- and 1,4-Silyl-Substituted Naphthalene Derivatives

Photoreactions of (2-Acetoxyphenyl)pentamethyldisilane

Steric Effects of Silyl Groups

Contact Info

Product

Resources

About