红移型Cu(II)离子比率荧光探针的光物理性质

引用本文: 崔俐丽, 周丹红, 李苗苗. 红移型Cu(II)离子比率荧光探针的光物理性质[J]. 物理化学学报, doi: 10.3866/PKU.WHXB201302064 shu

Citation: CUI Li-Li, ZHOU Dan-Hong, LI Miao-Miao. Photophysical Properties of a Red-Shift Cu(II) Ratiometric Fluorescent Chemosensor[J]. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB201302064 shu

红移型Cu(II)离子比率荧光探针的光物理性质

摘要:

应用密度泛函理论(DFT)及含时密度泛函理论(TDDFT)方法研究了N-丁基-4,5-二[2-(苯胺基)乙胺基]-l,8萘酰亚胺红移型铜离子比率荧光探针的光物理性质. 通过探针分子与金属离子结合前后的几何构型优化, 结合自然键轨道分析, 揭示了探针分子对铜离子的识别作用. 通过激发态计算阐明了光诱导分子内电荷转移(ICT)机理. 研究结果表明, 由于Cu(II)离子络合导致萘胺脱氢, 带负电荷的胺基N原子与萘环形成C＝N双键,延长了共轭体系; N的非键电子向Cu(II)离子的空d轨道转移一个电子, 抑制了Cu(II)离子的顺磁效应所导致的荧光淬灭, 受光激发后, 共轭N与萘环之间发生n→π^*电子转移导致ICT效应和荧光红移.

关键词:

English

Photophysical Properties of a Red-Shift Cu(II) Ratiometric Fluorescent Chemosensor

1.
Institute of Chemistry for Functionalized Materials, College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China
Received Date: 28 November 2012
Available Online: 25 March 2013

Abstract:

Density functional theory (DFT) and time-dependent DFT (TDDFT) were used to study the photophysical properties of N-butyl-4,5-di[2-(phenylamino)ethylamino]-1,8-naphthalimide, a ratiometric fluorescent sensor for Cu(II). The geometric structures of the compounds at the ground state were optimized by DFT. Combined with natural bond orbital (NBO) analysis, the binding characteristics of the chemosensor molecule coordinated with a Cu(II) ion were identified. The excitation states of the compounds were investigated and the internal charge transfer (ICT) mechanism was elucidated by theoretical calculations. The results indicated that the coordinated Cu(II) ion induced the dehydrogenation of naphthylamine. The negatively-charged amino N atom then formed a C＝N double bond with the naphthalene ring, extending the conjugation of the system. The nonbonding electron of N was transferred to the unoccupied d orbital of Cu(II), preventing fluorescence quenching by paramagnetic Cu(II). It was proposed that in the excited state, n→π^* electron transfer from the amino N to the naphthalene ring led to internal charge transfer and resulted in the red shift of fluorescence.

Key words:

4,5-Di(alkylamino)-1,8-naphthalimide
/ Copper ion fluorescent chemosensor
/ Internal charge transfer
/ Red-shift in fluorescence spectrum
/ Time-dependent density function theory

1. [1]
  
  (1) Tapiero,H.; Townsend,D.M.; Tew,K.D. Biomed. Pharmacother2003, 57, 386. doi: 10.1016/S0753-3322(03)00012-X
  (1) Tapiero,H.; Townsend,D.M.; Tew,K.D. Biomed. Pharmacother2003, 57, 386. doi: 10.1016/S0753-3322(03)00012-X
2. [2]
  (2) Linder, M. C.; Hazegh-Azam, M. Am. J. Clin. Nutr. 1996, 63,797S.(2) Linder, M. C.; Hazegh-Azam, M. Am. J. Clin. Nutr. 1996, 63,797S.
3. [3]
  (3) Uauy, R.; Olivares, M.; nzalez, M. Am. J. Clin. Nutr. 1998,67 (suppl), 952S.(3) Uauy, R.; Olivares, M.; nzalez, M. Am. J. Clin. Nutr. 1998,67 (suppl), 952S.
4. [4]
  (4) Rurack, K. Spectrochim. Acta A 2001, 57 (11), 2161. doi: 10.1016/S1386-1425(01)00492-9(4) Rurack, K. Spectrochim. Acta A 2001, 57 (11), 2161. doi: 10.1016/S1386-1425(01)00492-9
5. [5]
  (5) Zheng, Y. J.; Orbulescu, J.; Ji, X. J.; Andreopoulos, F. M.;Pham, S. M.; Leblanc, R. M. J. Am. Chem. Soc. 2003, 125,2680. doi: 10.1021/ja0293610(5) Zheng, Y. J.; Orbulescu, J.; Ji, X. J.; Andreopoulos, F. M.;Pham, S. M.; Leblanc, R. M. J. Am. Chem. Soc. 2003, 125,2680. doi: 10.1021/ja0293610
6. [6]
  (6) Hou, F. P.; Huang, L.; Xi, P. X.; Cheng, J.; Zhao, X. F.; Xie, G.Q.; Shi, Y. J.; Cheng, F. J.; Yao, X. J.; Bai, D. C.; Zeng, Z. Z.Inorg. Chem. 2012, 51, 2454. doi: 10.1021/ic2024082(6) Hou, F. P.; Huang, L.; Xi, P. X.; Cheng, J.; Zhao, X. F.; Xie, G.Q.; Shi, Y. J.; Cheng, F. J.; Yao, X. J.; Bai, D. C.; Zeng, Z. Z.Inorg. Chem. 2012, 51, 2454. doi: 10.1021/ic2024082
7. [7]
  (7) Zhou, Y. M.; Zhang, J. L.; Zhou, H.; Zhang, Q. Y.; Ma, T. S.;Niu, J. Y. Journal of Luminescence 2012, 132, 1837. doi: 10.1016/j.jlumin.2012.03.016(7) Zhou, Y. M.; Zhang, J. L.; Zhou, H.; Zhang, Q. Y.; Ma, T. S.;Niu, J. Y. Journal of Luminescence 2012, 132, 1837. doi: 10.1016/j.jlumin.2012.03.016
8. [8]
  (8) Kaur, S.; Kumar, S. Chem. Commun. 2002, 2840.(8) Kaur, S.; Kumar, S. Chem. Commun. 2002, 2840.
9. [9]
  (9) Banthia, S.; Samanta, A. J. Phys. Chem. B 2002, 106 (21), 5572.doi: 10.1021/jp014546z(9) Banthia, S.; Samanta, A. J. Phys. Chem. B 2002, 106 (21), 5572.doi: 10.1021/jp014546z
10. [10]
  (10) Mashraqui, S. H.; Chandiramani, M.; Betkar, R.; Ghorpade, S.Sensors and Actuators B 2010, 150, 574. doi: 10.1016/j.snb.2010.08.037(10) Mashraqui, S. H.; Chandiramani, M.; Betkar, R.; Ghorpade, S.Sensors and Actuators B 2010, 150, 574. doi: 10.1016/j.snb.2010.08.037
11. [11]
  (11) Xu, Z. C.; Pan, J.; Spring, D. R.; Cui, J. N.; Yoon, J. Y.Tetrahedron 2010, 66, 1678. doi: 10.1016/j.tet.2010.01.008(11) Xu, Z. C.; Pan, J.; Spring, D. R.; Cui, J. N.; Yoon, J. Y.Tetrahedron 2010, 66, 1678. doi: 10.1016/j.tet.2010.01.008
12. [12]
  (12) Zhu, H.; Fan, J. L.; Lu, J.; Hu, M. M.; Cao, J. F.;Wang, J.; Li,H. L.; Liu, X. J.; Peng, X. J. Talanta 2012, 93, 55. doi: 10.1016/j.talanta.2012.01.024(12) Zhu, H.; Fan, J. L.; Lu, J.; Hu, M. M.; Cao, J. F.;Wang, J.; Li,H. L.; Liu, X. J.; Peng, X. J. Talanta 2012, 93, 55. doi: 10.1016/j.talanta.2012.01.024
13. [13]
  (13) Fan, J. L.; Liu, X. J.; Hu, M. M.; Zhu, H.; Song, F. L.; Peng, X.J. Analytica Chimica Acta 2012, 735, 107. doi: 10.1016/j.aca.2012.05.027(13) Fan, J. L.; Liu, X. J.; Hu, M. M.; Zhu, H.; Song, F. L.; Peng, X.J. Analytica Chimica Acta 2012, 735, 107. doi: 10.1016/j.aca.2012.05.027
14. [14]
  (14) Zhao, T. F.; Zhao, D. F.; Yu, H. Y.; Cheng, L. B. DyestuffIndustry 1997, 34 (1), 8. [赵同丰, 赵德丰, 于华云, 程侣柏.染料工业, 1997, 34 (1), 8.](14) Zhao, T. F.; Zhao, D. F.; Yu, H. Y.; Cheng, L. B. DyestuffIndustry 1997, 34 (1), 8. [赵同丰, 赵德丰, 于华云, 程侣柏.染料工业, 1997, 34 (1), 8.]
15. [15]
  (15) Xu, Z. C.; Xiao, Y.; Qian, X. H.; Cui, J. N.; Cui, D.W. Org.Lett. 2005, 7 (5), 889. doi: 10.1021/ol0473445(15) Xu, Z. C.; Xiao, Y.; Qian, X. H.; Cui, J. N.; Cui, D.W. Org.Lett. 2005, 7 (5), 889. doi: 10.1021/ol0473445
16. [16]
  (16) Xu, Z. C.; Qian, X. H.; Cui, J. N. Org. Lett. 2005, 7 (14), 3029.doi: 10.1021/ol051131d(16) Xu, Z. C.; Qian, X. H.; Cui, J. N. Org. Lett. 2005, 7 (14), 3029.doi: 10.1021/ol051131d
17. [17]
  (17) Furche, F.; Rappoport, D. J. Am. Chem. Soc. 2004, 126 (4),1277. doi: 10.1021/ja037806u(17) Furche, F.; Rappoport, D. J. Am. Chem. Soc. 2004, 126 (4),1277. doi: 10.1021/ja037806u
18. [18]
  (18) Duan, X. H.; Li, X. Y.; He, R. X.; Cheng, X. M. J. Chem. Phys.2005, 122 (8), 084314. doi: 10.1063/1.1850097(18) Duan, X. H.; Li, X. Y.; He, R. X.; Cheng, X. M. J. Chem. Phys.2005, 122 (8), 084314. doi: 10.1063/1.1850097
19. [19]
  (19) Demeter, A.; Bérces, T.; Biczók, L.;Wintgens, V.; Valat, P.;Kossanyi, J. J. Phys. Chem. 1996, 100 (6), 2001. doi: 10.1021/jp951133n(19) Demeter, A.; Bérces, T.; Biczók, L.;Wintgens, V.; Valat, P.;Kossanyi, J. J. Phys. Chem. 1996, 100 (6), 2001. doi: 10.1021/jp951133n
20. [20]
  (20) Duan, X. H.; Pei, Z. H.; Ma, Y. J. Science in China Series B:Chemistry 2008, 38 (3), 232. [段晓惠, 裴重华, 马拥军.中国科学B辑: 化学, 2008, 38 (3), 232.](20) Duan, X. H.; Pei, Z. H.; Ma, Y. J. Science in China Series B:Chemistry 2008, 38 (3), 232. [段晓惠, 裴重华, 马拥军.中国科学B辑: 化学, 2008, 38 (3), 232.]
21. [21]
  (21) Paul, B. K.; Samanta, A.; Kar, S.; Guchhait, N. Journal ofLuminescence 2010, 130 (7), 1258. doi: 10.1016/j.jlumin.2010.02.036(21) Paul, B. K.; Samanta, A.; Kar, S.; Guchhait, N. Journal ofLuminescence 2010, 130 (7), 1258. doi: 10.1016/j.jlumin.2010.02.036
22. [22]
  (22) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913(22) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
23. [23]
  (23) Foster, J. P.;Weinhold, F. J. Am. Chem. Soc. 1980, 102 (24),7211. doi: 10.1021/ja00544a007(23) Foster, J. P.;Weinhold, F. J. Am. Chem. Soc. 1980, 102 (24),7211. doi: 10.1021/ja00544a007
24. [24]
  (24) Gross, E. K. U.; Kohn,W. Physical Review Letters 1985, 55 (26), 2850. doi: 10.1103/PhysRevLett.55.2850(24) Gross, E. K. U.; Kohn,W. Physical Review Letters 1985, 55 (26), 2850. doi: 10.1103/PhysRevLett.55.2850
25. [25]
  (25) Stratmann, R. E.; Scuseria, G. E.; Frisch, M. J. J. Chem. Phys.1998, 109, 8218. doi: 10.1063/1.477483(25) Stratmann, R. E.; Scuseria, G. E.; Frisch, M. J. J. Chem. Phys.1998, 109, 8218. doi: 10.1063/1.477483
26. [26]
  (26) Cossi, M.; Rega, N.; Scalmani, G.; Barone, V. J. Chem. Phys.2001, 114, 5691.(26) Cossi, M.; Rega, N.; Scalmani, G.; Barone, V. J. Chem. Phys.2001, 114, 5691.
27. [27]
  (27) Wang, Y. L.;Wu, G. S. Acta Phys. -Chim. Sin. 2008, 24, 552.[王溢磊, 吴国是. 物理化学学报, 2008, 24, 552.] doi: 10.1016/S1872-1508(08)60021-2(27) Wang, Y. L.;Wu, G. S. Acta Phys. -Chim. Sin. 2008, 24, 552.[王溢磊, 吴国是. 物理化学学报, 2008, 24, 552.] doi: 10.1016/S1872-1508(08)60021-2
28. [28]
  (28) Zhang, J. B.; Jin, L.; Zhang, H. X. Acta Phys. -Chim. Sin. 2011,27, 1089. [张建坡, 金丽, 张红星. 物理化学学报, 2011, 27,1089.] doi: 10.3866/PKU.WHXB20110505(28) Zhang, J. B.; Jin, L.; Zhang, H. X. Acta Phys. -Chim. Sin. 2011,27, 1089. [张建坡, 金丽, 张红星. 物理化学学报, 2011, 27,1089.] doi: 10.3866/PKU.WHXB20110505
29. [29]
  (29) Liu, X. J.; Lin, T.; Gao, S.W.; Ma, R.; Zhang, J. Y.; Cai, X. C.;Yang, L.; Teng, F. Acta Phys. -Chim. Sin. 2012, 28, 1337.[刘小君, 林涛, 高少伟, 马睿, 张晋悦, 蔡新晨, 杨磊,滕枫. 物理化学学报, 2012, 28, 1337.] doi: 10.3866/PKU.WHXB201204092(29) Liu, X. J.; Lin, T.; Gao, S.W.; Ma, R.; Zhang, J. Y.; Cai, X. C.;Yang, L.; Teng, F. Acta Phys. -Chim. Sin. 2012, 28, 1337.[刘小君, 林涛, 高少伟, 马睿, 张晋悦, 蔡新晨, 杨磊,滕枫. 物理化学学报, 2012, 28, 1337.] doi: 10.3866/PKU.WHXB201204092
30. [30]
  (30) Becke, A. D. Phys. Rev. A 1988, 38 (6), 3098. doi: 10.1103/PhysRevA.38.3098(30) Becke, A. D. Phys. Rev. A 1988, 38 (6), 3098. doi: 10.1103/PhysRevA.38.3098
31. [31]
  (31) Vosko, S. H.;Wilk, L.; Nusair, M. Canadian Journal of Physics1980, 58, 1200.(31) Vosko, S. H.;Wilk, L.; Nusair, M. Canadian Journal of Physics1980, 58, 1200.
32. [32]
  (32) Xu,W. H.; Zhang, Y.; Liu,W. J. Science in China Series B:Chemistry 2009, 39 (11), 1484. [许文华, 张勇, 刘文剑.中国科学B辑: 化学, 2009, 39 (11), 1484.](32) Xu,W. H.; Zhang, Y.; Liu,W. J. Science in China Series B:Chemistry 2009, 39 (11), 1484. [许文华, 张勇, 刘文剑.中国科学B辑: 化学, 2009, 39 (11), 1484.]
33. [33]
  (33) Perdew, J. P. Phys. Rev. B 1986, 33, 8832.(33) Perdew, J. P. Phys. Rev. B 1986, 33, 8832.
34. [34]
  (34) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03,Revision E.01; Gaussian Inc.:Wallingford, CT, 2004.(34) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03,Revision E.01; Gaussian Inc.:Wallingford, CT, 2004.
35. [35]
  (35) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B. et al. Gaussian 09,Revision B.01; Gaussian Inc.:Wallingford, CT, 2010.(35) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B. et al. Gaussian 09,Revision B.01; Gaussian Inc.:Wallingford, CT, 2010.
36. [36]
  (36) Wang, F. J.; Zhou, D. H.; Zuo, S. Y.; Cao, J. F.; Peng, X. J. ActaPhys. -Chim. Sin. 2012, 28, 1645. [王凤娇, 周丹红, 左士颖,曹建芳, 彭孝军. 物理化学学报, 2012, 28, 1645.] doi: 10.3866/PKU.WHXB201205083
  (36) Wang, F. J.; Zhou, D. H.; Zuo, S. Y.; Cao, J. F.; Peng, X. J. ActaPhys. -Chim. Sin. 2012, 28, 1645. [王凤娇, 周丹红, 左士颖,曹建芳, 彭孝军. 物理化学学报, 2012, 28, 1645.] doi: 10.3866/PKU.WHXB201205083

扫一扫看文章

计量

PDF下载量: 1271
文章访问数: 1322
HTML全文浏览量: 16

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

红移型Cu(II)离子比率荧光探针的光物理性质

English

Photophysical Properties of a Red-Shift Cu(II) Ratiometric Fluorescent Chemosensor

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

红移型Cu(II)离子比率荧光探针的光物理性质

English

Photophysical Properties of a Red-Shift Cu(II) Ratiometric Fluorescent Chemosensor

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs