间位取代卟啉及其锌卟啉的电子吸收光谱

doi:10.3866/PKU.WHXB201203024

物理化学学报 >> 2012, Vol. 28 >> Issue (05): 1085-1093.doi: 10.3866/PKU.WHXB201203024

间位取代卟啉及其锌卟啉的电子吸收光谱

曹振锋, 陈启斌, 卢运祥, 刘洪来, 胡英

华东理工大学, 结构可控先进功能材料及其制备教育部重点实验室, 上海 200237

收稿日期:2011-12-12 修回日期:2012-02-29 发布日期:2012-04-26
通讯作者: 陈启斌 E-mail:qibinchen@ecust.edu.cn
基金资助:
国家自然科学基金(20806025, 21103047)和中国高校111计划(B08021)资助项目

Electronic Absorption Spectra of Meso-Substituted Porphyrins and Their Zinc Derivatives

CAO Zhen-Feng, CHEN Qi-Bin, LU Yun-Xiang, LIU Hong-Lai, HU Ying

Key Laboratory for Advanced Material and Development of Chemistry, East China University of Science and Technology, Shanghai 200237, P. R. China

Received:2011-12-12 Revised:2012-02-29 Published:2012-04-26
Contact: CHEN Qi-Bin E-mail:qibinchen@ecust.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (20806025, 21103047) and National 111 Project of China's Higher Education (B08021).

摘要/Abstract

摘要： 取代的卟啉类衍生物在气敏传感器方面具有广泛的应用前景. 本文采用了密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)研究了四种不同取代基的卟啉衍生物(meso 位四硝基苯基/四氨基苯基卟啉(NO₂PP,NH₂PP)及其相应的锌金属卟啉衍生物(NO₂ZnPP, NH₂ZnPP))的紫外和近紫外光谱特征. 利用两种不同的交换相关泛函(广义梯度近似泛函(PBE)和杂化密度泛函(B3LYP))优化了上述四种物质的结构, 并应用TD-DFT计算了相应的电子激发能量和振动强度. 结果表明, 取代卟啉的吸收光谱与大量的电子跃迁有关; 与B3LYP泛函预测的光谱相比, PBE泛函所得B带以及Q带的波长位置与实验值更为接近. 另外, 计算所得硝基取代基卟啉的B带相对于氨基取代基卟啉的B带发生了红移, 这与实验现象也保持一致. 由于卟啉衍生物的三重激发态在电子转移中有很重要的应用, 因此在PBE/6-31G(d)水平上计算了四种物质的最低三重激发态能量, 分别为1.426、1.469、1.608和1.581 eV.

关键词: 含时密度泛函理论, 电子吸收光谱, 电子跃迁, 红移, 三重激发态

Abstract: Meso-substituted porphyrin derivatives have demonstrated great potential as sensing materials for toxic gas detection. In this paper, density functional theory (DFT) and its time-dependent DFT approach (TD-DFT) were employed to investigate the ultraviolet-visible (UV-Vis) or the near-ultravioletvisible (near-UV-Vis) absorption spectra of Meso-tetra (o-nitrophenyl/o-aminophenyl) porphyrins (NO₂PP, NH₂PP) and their corresponding zinc derivatives, NO₂ZnPP and NH₂ZnPP. The geometry optimizations for these four molecules were obtained from two different exchange-correlation functionals, the generalizedgradient approximation functional PBE (Perdew-Burke-Ernzerhof) and the hybrid functional B3LYP (Becke, three-parameter, Lee-Yang-Parr). The excitation energies and oscillation strengths were obtained from TD-DFT calculations. Calculations show that the optical absorptions are associated with numerous electronic transitions. In addition, the PBE-predicted wavelengths of the B and Q bands are more consistent with experiment than those predicted by B3LYP. The B band of NO₂-substituted derivative exhibits a bathochromic shift different from that of NH₂-containing material, also consistent with experimental results. In addition, at the PBE/6-31G(d) level of theory, the calculated energies of the lowest triplet excited states of NO₂PP, NH₂PP, NO₂ZnPP, and NH₂ZnPP are 1.426, 1.469, 1.608, and 1.581 eV, respectively.

Key words: TD-DFT, Electronic absorption spectrum, Electronic transition, Bathochromic shift, Triplet state

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曹振锋, 陈启斌, 卢运祥, 刘洪来, 胡英. 间位取代卟啉及其锌卟啉的电子吸收光谱[J]. 物理化学学报, 2012, 28(05), 1085-1093. doi: 10.3866/PKU.WHXB201203024

CAO Zhen-Feng, CHEN Qi-Bin, LU Yun-Xiang, LIU Hong-Lai, HU Ying. Electronic Absorption Spectra of Meso-Substituted Porphyrins and Their Zinc Derivatives[J]. Acta Phys. -Chim. Sin. 2012, 28(05), 1085-1093. doi: 10.3866/PKU.WHXB201203024

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201203024

https://www.whxb.pku.edu.cn/CN/Y2012/V28/I05/1085

参考文献

(1) Lanzo, I.; Russo, N.; Sicilia, E. J. Phys. Chem. B 2008, 112, 4123.

(2) Petsalakis, I. D.; Tagmatarchis, N.; Theodorakopoulos, G. J. Phys. Chem. C 2007, 111, 14139.

(3) Liao, M. S.; Watts, J. D.; Huang, M. J. J. Phys. Chem. A 2006, 110, 13089.

(4) Hasegawa, J.; Ohkawa, Y.; Hada, M.; Nakatsuji, H. J. Phys. Chem. B 1998, 102, 1320.

(5) Ricciardi, G.; Rosa, A.; Baerends, E. J.; van Gisbergen, S. A. J. J. Am. Chem. Soc. 2002, 124, 12319.

(6) Rubio, M.; Roos, B. O.; Serrano-Andrés, L.; Merchán, M. J. Chem. Phys. 1999, 110, 7202.

(7) Gouterman, M. The Porphyrins; Dolphin, D. Ed.; Academic Press, New York, 1978; Vol. 3, pp 1–165.
(8) Sundholm, D. Chem. Phys. Lett. 1999, 302, 480.

(9) Walsh, P. J.; Gordon, K. C.; Officer, D. L.; Campbell, W. M. J. Mol. Struct . -Theochem 2006, 759, 17.

(10) Galasso, V.; Kovac, B.; Modelli, A. Chem. Phys. 2007, 335, 141.

(11) Xu, S. C.; Zhang, H. J.; Sun, Z. Y.; Feng, J.; Ai, X. C.; Zhang, Q. Y.; Zhang, X. K. Acta Phys. -Chim. Sin. 2001, 17, 879. [徐四川, 张慧娟, 孙照勇, 冯娟, 艾希成, 张启元, 张兴康, 刘彦钦, 韩士田. 物理化学学报, 2001, 17, 879.]
(12) Li, Y.; Han, W. W.; Liao, M. X. Acta Phys. -Chim. Sin. 2009, 25, 2493. [李晔, 韩伟伟, 廖明霞. 物理化学学报, 2009, 25, 2493.]
(13) Ren, X. F.; Ren, A. M.; Wang, Q.; Feng, J. K. Acta Phys. -Chim. Sin. 2010, 26, 110. [任雪峰, 任爱民, 王钦, 封继康. 物理化学学报, 2010, 26, 110.]
(14) Ma, R. M.; Guo, P.; Yang, L. L.; Guo, L. S.; Zhang, X. X.; Nazeeruddin, M. K.; Grätzel, M. J. Phys. Chem. A 2010, 114, 1973.

(15) Cramariuc, O.; Hukka, T. I.; Rantala, T. T.; Lemmetyinen, H. J. Phys. Chem. A 2006, 110, 12470.

(16) Dunbar, A. D. F.; Richardson, T. H.; McNaughton, A. J.; Hutchinson, J.; Hunter, C. A. J. Phys. Chem. B 2006, 110, 16646.

(17) Dunbar, A. D. F.; Richardson, T. H.; Hutchinson, J.; Hunter, C. A. Sens. Actuators, B 2008, 128, 468.

(18) Chen, M.; Schliep, M.; Willows, R. D.; Cai, Z. I.; Neilan, B. A.; Scheer, H. Science 2010, 329, 1318.

(19) Sakakibara, K.; Ogawa, Y.; Nakatsubo, F. Macromol. Rapid Commun. 2007, 28, 1270.

(20) Dunbar, A. D. F.; Brittle, S.; Richardson, T. H.; Hutchinson, J.; Hunter, C. A. J. Phys. Chem. B 2010, 114, 11697.

(21) Wang, C. W.; Ren Y. J.; Cao, Z. F.; Chen, Q. B. Chem. Res. Chin. Univ. 2010, 26, 761.
(22) Sundholm, D. Phys. Chem. Chem. Phys. 2000, 2, 2275.
(23) Nguyen, K. A.; Day, P. N.; Pachter, R. J. Chem. Phys. 1999, 110, 9135.

(24) Gouterman, M. J. Mol. Spectrosc. 1961, 6, 138.

(25) Gouterman, M.; Wagniére, G. H. J. Mol. Spectrosc. 1963, 11, 108.

(26) Gouterman, M. J. Chem. Phys. 1959, 30, 1139.

(27) David, D.; Minh, T. N. Chem. Phys. Lett. 2003, 376, 329.

(28) Van Gisbergen, S. J. A, Rosa, A.; Ricciardi, G.; Baerends, E. J. J. Chem. Phys. 1999, 11, 2499.
(29) Nguyen, K. A.; Day, P. N.; Pachter, R. J. Phys. Chem. A 2000, 104, 4748.

(30) Adler, A. D.; Longo, F. R.; Kampas, F.; Kim, J. J. Inorg. Nucl. Chem. 1970, 32, 2443.

(31) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B 1992, 46, 6671.

(32) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865.

(33) Slater, J. C. Phys. Rev. 1951, 81, 385.

(34) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.

(35) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.

(36) Sundholm, D. Chem. Phys. Lett. 2000, 317, 392.

(37) Nguyen, K. A.; Pachter, R. J. Chem. Phys. 2001, 114, 10757.

(38) Seminario, J. M. Recent Developments and Applications of Modern Density Functional Theory; Elsevier: New York, 1996.
(39) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al. Gaussian 03, Revision D.01; Gaussian Inc.: Wallingford, CT, 2004
(40) Li, X.Y.; Czernuszewicz, R. S.; Kincaid, J. R.; Su, Y. O.; Spiro, T. G. J. Phys. Chem. 1990, 94, 31.

(41) Susi, H.; Ard, J. S. Spectrochim. Acta. A 1977, 33, 561.

(42) Scheidt, W. R.; Molfort, J. U.; Eigenbrot, C. W.; Adler, A.; Radonovich, L. J.; Hoard, J. L. Inorg.Chem. 1986, 25, 795.

(43) Prendergast, K.; Spiro, T. G. J. Am. Chem. Soc. 1992, 114, 3793.

(44) Koch, W.; Holthausen, M. C. A Chemist’s Guide to Density Functional Theory; Wiley-VCH: New York, 2001.

(45) Ernzerhof, M.; Perdew, J. P.; Burke, K. Density Functional Theory; Nalewajski, R. Ed. Spinger-Verlag: Berlin, 1996
(46) Ohkubo, K.; Imahori, H.; Shao, J.; Ou, Z.; Kadish, K. M.; Chen, Y.; Zheng, G.; Pandey, R. K.; Fujitsuka, M.; Ito, O.; Fukuzumi, S. J. Phys. Chem. A 2002, 106, 10991.

(47) Fukuzumi, S.; Ohkubo, K.; E, W. B.; Ou, Z. P.; Shao, J.; Kadish, K. M.; Hutchison, J. A.; Ghiggino, K. P.; Sintic, P. J.; Crossley, M. J. J. Am. Chem. Soc. 2003, 125, 14986.

(48) Luo, C.; Guldi, D. M.; Imahori, H.; Tamaki, K.; Sakata, Y. J. Am. Chem. Soc. 2000, 122, 6535.

(49) Cramariuc, O.; Hukka, T. I.; Rantala, T. T. J. Phys. Chem. A 2004, 108, 9435.

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间位取代卟啉及其锌卟啉的电子吸收光谱

Electronic Absorption Spectra of Meso-Substituted Porphyrins and Their Zinc Derivatives

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