Solvent dependent photocyclization and photophysics of some 2-ethynylbiphenyls

Frederick D. Lewis; Paul C. Karagiannis; Meledathu C. Sajimon; Katherine S. Lovejoy; Xiaobing Zuo; Michael Rubin; Vladimir Gevorgyan

doi:10.1039/b601751g

Solvent dependent photocyclization and photophysics of some 2-ethynylbiphenyls

Frederick D. Lewis, Paul C. Karagiannis, Meledathu C. Sajimon, Katherine S. Lovejoy, Xiaobing Zuo, Michael Rubin, Vladimir Gevorgyan

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

The spectroscopic properties and photochemical behavior of molecules having 2-ethynylbiphenyl or 2-phenyldiphenylacetylene structures are reported. These molecules undergo photocyclization reactions to yield phenanthrene and dihydrophenanthrene products via putative isophenanthrene (cyclic allene) intermediates. Phenanthrene formation from the isophenanthrene intermediates does not occur via a unimolecular sigmatropic hydrogen shift, but rather by protonation or hydrogen abstraction mechanisms involving the solvent. Cyclization efficiencies are much lower than is the case for previously-investigated 2-vinylbiphenyl systems. The 2-phenyldiphenylacetylenes have high fluorescence quantum yields and long singlet lifetimes when compared to diphenylacetylene. The 2-ethynylbiphenyls decay via a combination of fluorescence and intersystem crossing.

Original language	English (US)
Pages (from-to)	369-375
Number of pages	7
Journal	Photochemical and Photobiological Sciences
Volume	5
Issue number	4
DOIs	https://doi.org/10.1039/b601751g
State	Published - Apr 3 2006
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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title = "Solvent dependent photocyclization and photophysics of some 2-ethynylbiphenyls",

abstract = "The spectroscopic properties and photochemical behavior of molecules having 2-ethynylbiphenyl or 2-phenyldiphenylacetylene structures are reported. These molecules undergo photocyclization reactions to yield phenanthrene and dihydrophenanthrene products via putative isophenanthrene (cyclic allene) intermediates. Phenanthrene formation from the isophenanthrene intermediates does not occur via a unimolecular sigmatropic hydrogen shift, but rather by protonation or hydrogen abstraction mechanisms involving the solvent. Cyclization efficiencies are much lower than is the case for previously-investigated 2-vinylbiphenyl systems. The 2-phenyldiphenylacetylenes have high fluorescence quantum yields and long singlet lifetimes when compared to diphenylacetylene. The 2-ethynylbiphenyls decay via a combination of fluorescence and intersystem crossing.",

author = "Lewis, {Frederick D.} and Karagiannis, {Paul C.} and Sajimon, {Meledathu C.} and Lovejoy, {Katherine S.} and Xiaobing Zuo and Michael Rubin and Vladimir Gevorgyan",

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AU - Lewis, Frederick D.

AU - Karagiannis, Paul C.

AU - Sajimon, Meledathu C.

AU - Lovejoy, Katherine S.

AU - Zuo, Xiaobing

AU - Rubin, Michael

AU - Gevorgyan, Vladimir

PY - 2006/4/3

Y1 - 2006/4/3

N2 - The spectroscopic properties and photochemical behavior of molecules having 2-ethynylbiphenyl or 2-phenyldiphenylacetylene structures are reported. These molecules undergo photocyclization reactions to yield phenanthrene and dihydrophenanthrene products via putative isophenanthrene (cyclic allene) intermediates. Phenanthrene formation from the isophenanthrene intermediates does not occur via a unimolecular sigmatropic hydrogen shift, but rather by protonation or hydrogen abstraction mechanisms involving the solvent. Cyclization efficiencies are much lower than is the case for previously-investigated 2-vinylbiphenyl systems. The 2-phenyldiphenylacetylenes have high fluorescence quantum yields and long singlet lifetimes when compared to diphenylacetylene. The 2-ethynylbiphenyls decay via a combination of fluorescence and intersystem crossing.

AB - The spectroscopic properties and photochemical behavior of molecules having 2-ethynylbiphenyl or 2-phenyldiphenylacetylene structures are reported. These molecules undergo photocyclization reactions to yield phenanthrene and dihydrophenanthrene products via putative isophenanthrene (cyclic allene) intermediates. Phenanthrene formation from the isophenanthrene intermediates does not occur via a unimolecular sigmatropic hydrogen shift, but rather by protonation or hydrogen abstraction mechanisms involving the solvent. Cyclization efficiencies are much lower than is the case for previously-investigated 2-vinylbiphenyl systems. The 2-phenyldiphenylacetylenes have high fluorescence quantum yields and long singlet lifetimes when compared to diphenylacetylene. The 2-ethynylbiphenyls decay via a combination of fluorescence and intersystem crossing.

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Solvent dependent photocyclization and photophysics of some 2-ethynylbiphenyls

Abstract

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