2004
DOI: 10.1039/b412128g
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Photoreactions of cisoid 1,4-diphenyl-1,3-butadienes. Direct irradiation in solution and in low temperature organic glass

Abstract: The photoreactions of 1,4-diphenyl-1,3-butadienes (DPB) fused with a bicyclo[2.2.1]heptano ring under direct irradiation were examined in solution at room temperature and in organic glass at liquid nitrogen temperature. Photocyclization yielding a phenylnaphthalene compound was shown to be preceded by facile E,E to E,Z photoisomerization. The reverse E,Z to E,E isomerization took place with equal ease in low temperature organic glass and in solution at room temperature. The pattern of reaction at low temperatu… Show more

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Cited by 7 publications
(2 citation statements)
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“…BP and HT mechanisms are expected to reduce volume requirements associated with torsional relaxation by confining most of the motion to the vicinity of the isomerizing double bonds while minimizing the motion of bulky substituents. The HT mechanism has been claimed to account for photoisomerization of several olefins in amorphous glassy media at low temperatures. , Theoretical calculations suggest that 1,3-bond formation in the 2 1 A g states of polyenes at a conical intersection for ultrafast radiationless decay to the ground state may open a pathway to HT products. We reported recently that the photoisomerization of cis -1-(2-naphthyl)-2-phenylethene in methylcyclohexane glass at 77 K is conformer specific, giving the one bond twist ( OBT ) product as in solution . Direct cc- DPB to tt- DPB conversion is the only example, thus far, of the BP mechanism under similar conditions…”
Section: Introductionmentioning
confidence: 99%
“…BP and HT mechanisms are expected to reduce volume requirements associated with torsional relaxation by confining most of the motion to the vicinity of the isomerizing double bonds while minimizing the motion of bulky substituents. The HT mechanism has been claimed to account for photoisomerization of several olefins in amorphous glassy media at low temperatures. , Theoretical calculations suggest that 1,3-bond formation in the 2 1 A g states of polyenes at a conical intersection for ultrafast radiationless decay to the ground state may open a pathway to HT products. We reported recently that the photoisomerization of cis -1-(2-naphthyl)-2-phenylethene in methylcyclohexane glass at 77 K is conformer specific, giving the one bond twist ( OBT ) product as in solution . Direct cc- DPB to tt- DPB conversion is the only example, thus far, of the BP mechanism under similar conditions…”
Section: Introductionmentioning
confidence: 99%
“…A recent claim that the photoconversion of previtamin D to tachysterol at 92 K in a rigid glass (5/5/1 ether/isopentane/ethyl alcohol) is consistent with the HT mechanism may provide the first experimental demonstration of this process in an amorphous medium . It breathed new life into this concept and has motivated its revival . Experimental evidence appears to be strong for protein-bound chromophores, and the HT has captured the imagination of the photochemical community.…”
mentioning
confidence: 99%