Both direct and sensitized irradiations of the endo title compound lead to a decarbony- lation product,4-isopropylbiphenyl,via Norrish Type 1 reaction,while the exo isomer gives a carbene intermediate and subsequently...Both direct and sensitized irradiations of the endo title compound lead to a decarbony- lation product,4-isopropylbiphenyl,via Norrish Type 1 reaction,while the exo isomer gives a carbene intermediate and subsequently formaldehyde 2-biphenylyl isopropyl hemiacetal,which in turn gradually decomposes to dimethyl phenylbenzyl alcohol at room temperature.The triplet pathway dominates the photoreaction of the exo isomer.The singlet and triplet lifetimes of the reactant are found to be 0.29 ns and 5.4μs,respectively.~3(n,π~*),~1(n,π~*),~3(π,π~*)electronic configurations of the exo isomer and ~3(π,π~*)of the endo isomer are photochemically active,but ~1(π,π~*)of the endo isomer shows indirect photoreactivity.展开更多
The crystal structure of 5-{[(4′-heptoxy-biphenylyl-4-yl)oxy]carbonyl}-1-pentyne({A3E′O7}) was investigated by wide angle X-ray diffraction(WAXD), transmission electron microscope(TEM) and atom force microscope(AFM)...The crystal structure of 5-{[(4′-heptoxy-biphenylyl-4-yl)oxy]carbonyl}-1-pentyne({A3E′O7}) was investigated by wide angle X-ray diffraction(WAXD), transmission electron microscope(TEM) and atom force microscope(AFM). The structures of A3E′O7 solution-crystal and melt-crystal are the same. The crystals belong to the monoclinic P112/m space group, the cell parameters are {a0.589 nm}, b0^771 nm, c4.75 nm, αβ90° and γ93.8°, the calculated cell density is {1.167 g/cm+3}.展开更多
基金This project was supported by the National Natural Science Foundation of China.
文摘Both direct and sensitized irradiations of the endo title compound lead to a decarbony- lation product,4-isopropylbiphenyl,via Norrish Type 1 reaction,while the exo isomer gives a carbene intermediate and subsequently formaldehyde 2-biphenylyl isopropyl hemiacetal,which in turn gradually decomposes to dimethyl phenylbenzyl alcohol at room temperature.The triplet pathway dominates the photoreaction of the exo isomer.The singlet and triplet lifetimes of the reactant are found to be 0.29 ns and 5.4μs,respectively.~3(n,π~*),~1(n,π~*),~3(π,π~*)electronic configurations of the exo isomer and ~3(π,π~*)of the endo isomer are photochemically active,but ~1(π,π~*)of the endo isomer shows indirect photoreactivity.
文摘The crystal structure of 5-{[(4′-heptoxy-biphenylyl-4-yl)oxy]carbonyl}-1-pentyne({A3E′O7}) was investigated by wide angle X-ray diffraction(WAXD), transmission electron microscope(TEM) and atom force microscope(AFM). The structures of A3E′O7 solution-crystal and melt-crystal are the same. The crystals belong to the monoclinic P112/m space group, the cell parameters are {a0.589 nm}, b0^771 nm, c4.75 nm, αβ90° and γ93.8°, the calculated cell density is {1.167 g/cm+3}.
