二芳基乙烯光致变色理论研究
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摘要
闭环全氟二芳基乙烯对光较为敏感,在紫外光照射下会发生开环反应。利用密度泛函研究了全氟二芳基乙烯光致变色的初级光化学反应机理,基态条件下,全氟代环戊烯分子由开环到闭环需克服91.48kJ/mol的势垒,反应常温下较难发生,但在激发态时只需克服21.52 kJ/mol的势垒,其逆反应活化能更小只有9.29kJ/mol,故开环及闭环反应容易发生,与实验事实相符。
Closed-ring perfluorinated diarylene is very sensitive to light and it will occur the open-ring reaction under UV light irradiation. In this paper, the primary photochemical reaction mechanism of the diarylene about phototropy using density functional theory(DFT)the reaction from the open-ring configuration turning into closed-ring configuration of the perfluorinated diarylene is difficult at room temperature due to 91.48 kJ/mol potential barrier on the ground state, however the reaction is easy due to over 21.52 kJ/mol potential barrier on the excited state, and the activation energy of the reverse of reaction is only 9.29 kJ/mol, which enable the open-ring and closed-ring reaction to become easy and the calculated results are in agreement with the experiment.
Closed-ring perfluorinated diarylene is very sensitive to light and it will occur the open-ring reaction under UV light irradiation. In this paper, the primary photochemical reaction mechanism of the diarylene about phototropy using density functional theory(DFT)the reaction from the open-ring configuration turning into closed-ring configuration of the perfluorinated diarylene is difficult at room temperature due to 91.48 kJ/mol potential barrier on the ground state, however the reaction is easy due to over 21.52 kJ/mol potential barrier on the excited state, and the activation energy of the reverse of reaction is only 9.29 kJ/mol, which enable the open-ring and closed-ring reaction to become easy and the calculated results are in agreement with the experiment.
引文
[1]樊美公.光化学基本原理与光子材料[M].北京:科学出版社,2001:1-7.
[2]朱世琴,李文龙,朱为宏.新型烯桥二芳基乙烯光致变色体系[J].化学进展,2016,(28):975-992.
[3]邹祺,张隽佶,田禾.多功能二噻吩乙烯光致变色光分子开关材料[J].化学进展,2012,(24):1632-1645.
[4] KOBATAKE S,TAKAMI S,MUTO H,et alRapid and reversible shape changes of molecular crystals on photoirradiation[J].Nature,2007,(446):778-781.
[5] ANDREASSON J,PISCHEL U,STRAIGHT S D,et alAllphotonic multifunctional molecular logic device[J].Journal of the American Chemical Society,2011,(133):11641-11648.
[6] ORGIU E,CRIVILLERS N,HERDER M,et al.The gold-sulfur interface at the nanoscale[J].Nature Chemistry,2012,(4):443-455.
[7] GEMAYEL M E,BORJESSON K,HERDER M,et al.Optically switchable transistors by simple incorporation of photochromic systems into small-molecule semiconducting matrices[J].Nature Communication,2015,(6):6330-6333.
[8] FUKAMINATO T,HIROSE T,DOI T,et alMolecular design strategy toward diarylethenes that photoswitch with visible light[J].Journal of the American Chemical Society,2014,(136):17145-17154.
[9] WU C,TRETIAK S,CHERNYAK V Y.Excited states and op-tical response of a donor-acceptor substituted polyene:A TD-DFT study[J].Chemical Physics Letters,2007,433(7):30-35.
[10] OHSHITA J,KANGAI S,TADA Y,et al.Synthesis of diarylenenaphthylene-and diaryleneanthrylene containing organosilicon polymers and their applications to organic EL devices[J].Journal of Organometallic Chemistry,2007,(692):1020-1024.
[11] IRIE M,FUKAMINATO T,MATSUDA K,KOBATAKE S.Photochromism of diarylethene molecules and crystals[J].ChemicalReview,2014,(114):12174-12277.
[2]朱世琴,李文龙,朱为宏.新型烯桥二芳基乙烯光致变色体系[J].化学进展,2016,(28):975-992.
[3]邹祺,张隽佶,田禾.多功能二噻吩乙烯光致变色光分子开关材料[J].化学进展,2012,(24):1632-1645.
[4] KOBATAKE S,TAKAMI S,MUTO H,et alRapid and reversible shape changes of molecular crystals on photoirradiation[J].Nature,2007,(446):778-781.
[5] ANDREASSON J,PISCHEL U,STRAIGHT S D,et alAllphotonic multifunctional molecular logic device[J].Journal of the American Chemical Society,2011,(133):11641-11648.
[6] ORGIU E,CRIVILLERS N,HERDER M,et al.The gold-sulfur interface at the nanoscale[J].Nature Chemistry,2012,(4):443-455.
[7] GEMAYEL M E,BORJESSON K,HERDER M,et al.Optically switchable transistors by simple incorporation of photochromic systems into small-molecule semiconducting matrices[J].Nature Communication,2015,(6):6330-6333.
[8] FUKAMINATO T,HIROSE T,DOI T,et alMolecular design strategy toward diarylethenes that photoswitch with visible light[J].Journal of the American Chemical Society,2014,(136):17145-17154.
[9] WU C,TRETIAK S,CHERNYAK V Y.Excited states and op-tical response of a donor-acceptor substituted polyene:A TD-DFT study[J].Chemical Physics Letters,2007,433(7):30-35.
[10] OHSHITA J,KANGAI S,TADA Y,et al.Synthesis of diarylenenaphthylene-and diaryleneanthrylene containing organosilicon polymers and their applications to organic EL devices[J].Journal of Organometallic Chemistry,2007,(692):1020-1024.
[11] IRIE M,FUKAMINATO T,MATSUDA K,KOBATAKE S.Photochromism of diarylethene molecules and crystals[J].ChemicalReview,2014,(114):12174-12277.