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为了研究卟啉类敏化剂的光致激发态能量转移和电子转移问题，本文基于紫外可见光谱仪和电子顺磁共振波谱仪，构建了以锌卟啉为研究对象的“锌卟啉-稳态自由基-二甲苯”实验体系. 锌卟啉的紫外可见光谱显示，在可见光谱的B带和Q带出现明显的特征峰，是锌卟啉分子中电子由基态能级跃迁至激发态能级产生的. 低温条件下受紫外可见光辐照的实验体系的电子顺磁共振波谱，检测到了稳态自由基四甲基哌啶氧化物的增强吸收电子顺磁共振波谱. 根据分子激发态相关理论、光化学物理反应理论和化学诱导电子自旋极化理论对实验结果进行了分析，结果表明，四甲基哌啶氧化物稳态自由基电子顺磁共振波谱的增强吸收对应于锌卟啉光致激发态的能量转移和电子转移；四甲基哌啶氧化物在低温（143 K）下的电子顺磁共振波谱表现出的各向异性特征现象来源于氮氧自由基电子与氮核的各向异性超精细相互作用.To investigate the energy transfer and electron transfer of the photo-induced excited state in porphyrin sensitizers, we built the “zinc porphyrin-2, 2, 6, 6-tetramethylpiperidinooxy-xylene” experimental system. Zinc porphyrin's UV-visible spectrum shows that the characteristic absorption line of zinc porphyrin consists of bands B and Q, which are generated by the transition of elections from the ground state to the excited state in molecules of zinc porphyrin. The electron paramagnetic resonance spectrum of the experimental system is produced under the UV-visible light irradiation, at a temperature of 143 K; and we have detected the enhanced electron paramagnetic resonance spectrum of 2, 2, 6, 6-tetramethylpiperidinooxy. Based on the theory of the molecular excited states, and the photophysical and photochemical theory as well as the theory of the chemical-induced electron spin polarization, we also analyze the experimental results. Our conclusion is that the enhanced electron paramagnetic resonance spectrum of 2, 2, 6, 6-tetramethylpiperidinooxy is caused by the energy transfer and electron transfer of the photo-induced excited state in the porphyrin sensitizers. The anisotropic characteristics of the phenomenon of electron paramagnetic resonance spectrum of 2, 2, 6, 6-tetramethylpiperidinooxy at low temperatures are due to the anisotropic hyperfine interaction between nitroxide electrons and nitrogen nuclear.
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Keywords:
- ZnTPP /
- photo-induced excited state /
- UV-visible spectrum /
- electronic paramagnetic resonance
[1] Yu G X, Li D M, Qin D, Sun H C, Zhang Y D, Luo Y H, Meng Q B 2009 Materials China 2 8 (in Chinese)[于哲勋, 李冬梅, 秦达, 孙惠成, 张一多, 罗艳红, 孟庆波 2009 中国材料进展 2 8]
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[4] Zhao S L, Xu Z, Liu X D, Xu X R, Zhang T H, Piao L Y, Ju S T 2011 Chin. Phys. B 20 038401
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[6] Kristina N F, Tina M I, Karim M, James B, So I 2004 Science 303 1831
[7] Chen Y M, Wang Y X, Jiang L, Zhang X R, Yang J Y, Li Y L, Song Y L 2009 Acta Phys. Sin. 58 0995 (in Chinese)[陈玉明, 王玉晓, 蒋礼, 张学如, 杨俊义, 李玉良, 宋瑛林 2009 58 0995]
[8] Krzysztof O, Irena D, Yakov P N, Anna S H 2013 Polyhedron 51 61
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[15] Gouterman M 1963 J. Mol. Spectrosc. 5 108
[16] Shen G 2012 M.S. Dissertation (Xuzhou: China University of Mining and Technology) (in Chinese) [神干 2012 硕士学位论文(徐州: 中国矿业大学)]
[17] Zhang J Z 1987 The Fundamental of Spin Labeling the ESR Spectrum and its Application (Beijing: Beijing science and Technology Press) p34-104 (in Chinese) [张建中 1987 自旋标记ESR波谱的基本理论和应用(北京: 北京科学出版社)第34–104页]
[18] Liu Y C, Jiang Z Q, Wu S P 1980 Chem. J. Chin. U. 1 67 (in Chinese)[刘有成, 江致勤, 吴树屏 1980 高等学校化学学报 1 67]
[19] Yang G Y, Guo Y C, Wu G H, Zheng L W, Song M P 2007 Prog. Chem. 19 1727 (in Chinese)[杨贯羽, 郭彦春, 武光辉, 郑立稳, 宋毛平 2007 化学进展 19 1727]
[20] Zhang F, Liu Y C 1989 Acta Chim. Sin. 47 186 (in Chinese)[张发, 刘有成 1989 化学学报 47 186]
[21] Wang S L 2000 The Generalized Theory of Evolution (Changsha: Hunan Science & Technology Press) p195-198 (in Chinese) [王身立 2000 广义进化论(长沙: 湖南科学技术出版社)第195–198页]
[22] Pedersen J B, Freed J H 1975 The Journal of Phys. Chem. 62 1706
[23] Pedersen J B Freed J H 1973 The Journal of Phys. Chem. 58 2746
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[1] Yu G X, Li D M, Qin D, Sun H C, Zhang Y D, Luo Y H, Meng Q B 2009 Materials China 2 8 (in Chinese)[于哲勋, 李冬梅, 秦达, 孙惠成, 张一多, 罗艳红, 孟庆波 2009 中国材料进展 2 8]
[2] Daniel G 2012 Acc. Chem. Res. 45 767
[3] Wu D, Shen Z, Xue Z L, You X Z 2007 Chinese J. Inorg. Chem. 23 1 (in Chinese) [吴迪, 沈珍, 薛兆历, 游效曾 2007 无机化学学报 23 1]
[4] Zhao S L, Xu Z, Liu X D, Xu X R, Zhang T H, Piao L Y, Ju S T 2011 Chin. Phys. B 20 038401
[5] Shao H X, Liu R, Wu Q, Gao X R 2008 Med. Recapitulate 14 3404 (in Chinese) [邵红霞 2008 医学综述 14 3404]
[6] Kristina N F, Tina M I, Karim M, James B, So I 2004 Science 303 1831
[7] Chen Y M, Wang Y X, Jiang L, Zhang X R, Yang J Y, Li Y L, Song Y L 2009 Acta Phys. Sin. 58 0995 (in Chinese)[陈玉明, 王玉晓, 蒋礼, 张学如, 杨俊义, 李玉良, 宋瑛林 2009 58 0995]
[8] Krzysztof O, Irena D, Yakov P N, Anna S H 2013 Polyhedron 51 61
[9] Song B Q, Pan L D, Du S X, Gao H J 2013 Chin. Phys. B 22 096801
[10] Sun Y H, Wang C K 2011 Chin. Phys. B 20 101204
[11] Zhang X Y, Cui Z F, Xu X S, Lu T X 2000 Journal of Atomic and Molecular Physics 17 613 (in Chinese) [张先燚, 崔执凤, 许新胜, 陆同兴 2000 原子与分子 17 613]
[12] Wang M X, Li Q 2011 Chinese Journal of Spectroscopy 28 1165 (in Chinese) [王慢想, 李强 2011 光谱实验室 28 1165]
[13] Lu J F 2012 Advance Electron Paramagnetic Resonance Spectroscopy and its Application (Beijing: Peking University Medical Press) p141-142 (in Chinese) [卢景雰 2012 现代电子顺磁共振波谱学及其应用(北京: 北京大学医学出版社)第141–142页]
[14] Gouterman M 1961 J. Mol. Spectrosc. 14 138
[15] Gouterman M 1963 J. Mol. Spectrosc. 5 108
[16] Shen G 2012 M.S. Dissertation (Xuzhou: China University of Mining and Technology) (in Chinese) [神干 2012 硕士学位论文(徐州: 中国矿业大学)]
[17] Zhang J Z 1987 The Fundamental of Spin Labeling the ESR Spectrum and its Application (Beijing: Beijing science and Technology Press) p34-104 (in Chinese) [张建中 1987 自旋标记ESR波谱的基本理论和应用(北京: 北京科学出版社)第34–104页]
[18] Liu Y C, Jiang Z Q, Wu S P 1980 Chem. J. Chin. U. 1 67 (in Chinese)[刘有成, 江致勤, 吴树屏 1980 高等学校化学学报 1 67]
[19] Yang G Y, Guo Y C, Wu G H, Zheng L W, Song M P 2007 Prog. Chem. 19 1727 (in Chinese)[杨贯羽, 郭彦春, 武光辉, 郑立稳, 宋毛平 2007 化学进展 19 1727]
[20] Zhang F, Liu Y C 1989 Acta Chim. Sin. 47 186 (in Chinese)[张发, 刘有成 1989 化学学报 47 186]
[21] Wang S L 2000 The Generalized Theory of Evolution (Changsha: Hunan Science & Technology Press) p195-198 (in Chinese) [王身立 2000 广义进化论(长沙: 湖南科学技术出版社)第195–198页]
[22] Pedersen J B, Freed J H 1975 The Journal of Phys. Chem. 62 1706
[23] Pedersen J B Freed J H 1973 The Journal of Phys. Chem. 58 2746
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