红移型Cu(II)离子比率荧光探针的光物理性质

doi:10.3866/PKU.WHXB201302064

摘要/Abstract

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: 1,8-萘酰亚胺-4,5-胺基衍生物, 铜离子荧光分子探针, 分子内电荷转移, 荧光红移, 含时密度泛函理论

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

MSC2000:

O641

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, 2013, 29(04): 745-753.

CUI Li-Li, ZHOU Dan-Hong, LI Miao-Miao. Photophysical Properties of a Red-Shift Cu(II) Ratiometric Fluorescent Chemosensor[J]. Acta Phys. -Chim. Sin., 2013, 29(04): 745-753.

参考文献

(1) Tapiero,H.; Townsend,D.M.; Tew,K.D. Biomed. Pharmacother2003, 57, 386. doi: 10.1016/S0753-3322(03)00012-X
(2) Linder, M. C.; Hazegh-Azam, M. Am. J. Clin. Nutr. 1996, 63,797S.
(3) Uauy, R.; Olivares, M.; Gonzalez, M. Am. J. Clin. Nutr. 1998,67 (suppl), 952S.
(4) Rurack, K. Spectrochim. Acta A 2001, 57 (11), 2161. doi: 10.1016/S1386-1425(01)00492-9
(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) 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) 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) Kaur, S.; Kumar, S. Chem. Commun. 2002, 2840.
(9) Banthia, S.; Samanta, A. J. Phys. Chem. B 2002, 106 (21), 5572.doi: 10.1021/jp014546z
(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) 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) 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) 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) 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) 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) Xu, Z. C.; Qian, X. H.; Cui, J. N. Org. Lett. 2005, 7 (14), 3029.doi: 10.1021/ol051131d
(17) Furche, F.; Rappoport, D. J. Am. Chem. Soc. 2004, 126 (4),1277. doi: 10.1021/ja037806u
(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) Demeter, A.; Bérces, T.; Biczók, L.;Wintgens, V.; Valat, P.;Kossanyi, J. J. Phys. Chem. 1996, 100 (6), 2001. doi: 10.1021/jp951133n
(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) Paul, B. K.; Samanta, A.; Kar, S.; Guchhait, N. Journal ofLuminescence 2010, 130 (7), 1258. doi: 10.1016/j.jlumin.2010.02.036
(22) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
(23) Foster, J. P.;Weinhold, F. J. Am. Chem. Soc. 1980, 102 (24),7211. doi: 10.1021/ja00544a007
(24) Gross, E. K. U.; Kohn,W. Physical Review Letters 1985, 55 (26), 2850. doi: 10.1103/PhysRevLett.55.2850
(25) Stratmann, R. E.; Scuseria, G. E.; Frisch, M. J. J. Chem. Phys.1998, 109, 8218. doi: 10.1063/1.477483
(26) Cossi, M.; Rega, N.; Scalmani, G.; Barone, V. J. Chem. Phys.2001, 114, 5691.
(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) 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) 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) Becke, A. D. Phys. Rev. A 1988, 38 (6), 3098. doi: 10.1103/PhysRevA.38.3098
(31) Vosko, S. H.;Wilk, L.; Nusair, M. Canadian Journal of Physics1980, 58, 1200.
(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) Perdew, J. P. Phys. Rev. B 1986, 33, 8832.
(34) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03,Revision E.01; Gaussian Inc.:Wallingford, CT, 2004.
(35) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B. et al. Gaussian 09,Revision B.01; Gaussian Inc.:Wallingford, CT, 2010.
(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

[1]	卢浩然, 魏雅清, 龙闰. 纳米孔缺陷导致单层黑磷电荷局域极大抑制非辐射电子-空穴复合的时域模拟[J]. 物理化学学报, 2022, 38(5): 2006064 - .
[2]	冯诗语, 路皓, 刘泽坤, 刘亚辉, 李翠红, 薄志山. 通过非共价构象锁定和端基工程策略设计高效率的A-D-A型稠环电子受体[J]. 物理化学学报, 2019, 35(4): 355 -360 .
[3]	孙海涛,钟成,孙真荣. 最优化“调控”区间分离密度泛函理论的研究进展[J]. 物理化学学报, 2016, 32(9): 2197 -2208 .
[4]	尹海峰. 硅烯量子点二聚物的等离激元激发[J]. 物理化学学报, 2016, 32(6): 1446 -1452 .
[5]	郑东,袁相爱,马晶. 邻位甲基红水溶液的光谱性质随pH值的变化：含时密度泛函理论计算与实验研究[J]. 物理化学学报, 2016, 32(1): 290 -300 .
[6]	叶传香,马会利,梁万珍. 几个荧光蛋白发色团双光子吸收性质的理论研究[J]. 物理化学学报, 2016, 32(1): 301 -312 .
[7]	侯丽梅,温智,李银祥,胡华友,阚玉和,苏忠民. 含中氮茚有机太阳能电池染料敏化剂的分子设计[J]. 物理化学学报, 2015, 31(8): 1504 -1512 .
[8]	黄斌,代钰,班鑫鑫,蒋伟,张兆杭,孙开涌,林保平,孙岳明. 基于三苯胺/二苯砜的热激活延迟荧光材料[J]. 物理化学学报, 2015, 31(8): 1621 -1628 .
[9]	杨文静,张玉瑾,王传奎. 基于4-氨基-1, 8萘酰亚胺的双光子荧光H₂S探针光学性质与响应机理分析[J]. 物理化学学报, 2015, 31(12): 2303 -2309 .
[10]	尹海峰, 向功周, 岳莉, 张红. 硅烯量子点的等离激元激发[J]. 物理化学学报, 2015, 31(1): 67 -72 .
[11]	尹海峰, 张红, 岳莉. 氮掺杂六角石墨烯纳米结构的近红外等离激元研究[J]. 物理化学学报, 2014, 30(6): 1049 -1054 .
[12]	孙进, 梁万珍. 石墨烯条带的电子结构与性质:电场及长度效应[J]. 物理化学学报, 2014, 30(3): 439 -445 .
[13]	陈喜明, 贾春阳, 万中全, 姚小军. 四硫富瓦烯作为染料敏化太阳能电池有机染料电子给体的理论研究[J]. 物理化学学报, 2014, 30(2): 273 -280 .
[14]	凌欢欢, 李楠, 杨帆, 吉昕, 夏勇, 曹都, 祁争健. 新型2-取代苯基-1H-咪唑[4,5-f][1,10]邻菲啰啉基Ru(II)配合物的光电性质[J]. 物理化学学报, 2013, 29(11): 2465 -2474 .
[15]	周丹红, 李苗苗, 崔俐丽. 用于监控过氧化氮的近红外荧光探针的光物理性质及PET机理[J]. 物理化学学报, 2013, 29(07): 1453 -1460 .