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通过增强电荷转移激发态构建激发态下稳定的基于氰基二苯乙烯的E/Z构型(英文)
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作者 董玉杰 许晨东 +3 位作者 王士昭 李维军 宋庆宝 张诚 《物理化学学报》 SCIE CAS CSCD 北大核心 2019年第6期637-643,共7页
在前期工作中,我们报道了一个三苯胺基团键接氰基二苯基乙烯单元的分子TPNCF,并认为从局域激发态到电荷转移(CT)激发态的快速内转换,能够有效抑制E/Z异构化反应。为了进一步证明CT态能够诱导E/Z构型的稳定,本文中我们将三苯胺基团替代... 在前期工作中,我们报道了一个三苯胺基团键接氰基二苯基乙烯单元的分子TPNCF,并认为从局域激发态到电荷转移(CT)激发态的快速内转换,能够有效抑制E/Z异构化反应。为了进一步证明CT态能够诱导E/Z构型的稳定,本文中我们将三苯胺基团替代为给电子能力更强的吩噁嗪基团,设计合成了分子PZNCF,并且成功获得其E/Z异构体。通过对原位核磁及紫外光谱数据的分析,我们发现相比于TPNCF,PZNCF在光辐照下的E/Z异构化反应明显变慢。这说明对于氰基二苯基乙烯单元,一个更强给电子能力基团吩噁嗪的引入能够使其在激发态下具有更稳定的E/Z构型。密度泛函理论计算及光物理测试结果表明PZNCF分子具有较强的电荷转移激发态,这也更加证实了我们先前的结论:通过合理构建给受体结构,能够获得激发态下构型稳定的E/Z异构体。 展开更多
关键词 E/Z构型 电荷转移激发态 氰基二苯基乙烯 给受体结构 局域激发态
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Photophysical Properties of 4t-(p-aminophenyl)-2,2':6',2″-terpyridine
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作者 宋朋 孙士国 +3 位作者 周潘旺 刘建勇 徐勇前 彭孝军 《Chinese Journal of Chemical Physics》 SCIE CAS CSCD 2010年第5期558-564,622,共8页
Spectral and photophysical investigations of 4'-(p-aminophenyl)-2,2':6',2″-terpyridine (APT) have been performed in various solvents with different polarity and hydrogen-bonding ability. The emission spectra ... Spectral and photophysical investigations of 4'-(p-aminophenyl)-2,2':6',2″-terpyridine (APT) have been performed in various solvents with different polarity and hydrogen-bonding ability. The emission spectra of APT are found to exhibit dual fluorescence in polar solvents, which attributes to the local excited and intramolecular charge transfer states, respectively. The two-state model is proven out for APT in polar solvent by the time-correlated single photon counting emission decay measurement. Interestingly, the linear relationships of different emission maxima and solvent polarity parameter are found for APT in protic and aprotic solvents, because of the hydrogen bond formation between APT and alcohols at the amino nitrogen N25. Furthermore, the effects of the complexation of the metal ion with tpy group of APT and the hydrogen bond formation between APT with methanol at the terpyridine nitrogen N4-NS-N14 are also presented. The appearance of new long-wave absorption and fluorescence bands indicates that a new ground state of the complexes is formed. 展开更多
关键词 Dual fluorescence Local excited state Intramolecular charge transfer TERPYRIDINE COMPLEXATION Fluorescence decay
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