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采用密度泛函理论(DFT)和含时密度泛函理论(TDDFT)方法, 基于连续介质模型, 对HBT-OMe分子及其与HClO反应的产物基态和激发态结构及电荷分布等性质进行研究, 优化构型结果表明, HBT-OMe分子不能发生质子转移过程而其产物分子则能发生. 红外振动光谱与分子共价作用分析进一步证实产物分子能发生质子转移过程. 计算的前线分子轨道结果表明: HBT-OMe分子存在扭曲电荷转移(TICT)过程, 最高已占据分子轨道(HOMO)和最低未占据分子轨道(LUMO)电荷密度重叠小导致HBT-OMe分子荧光强度弱, 结合产物分子势能曲线发现, 产物分子质子转移过程能抑制分子的TICT过程, 从而使其荧光强度增强.The molecule with excited-state intramolecular proton transfer (ESIPT) has wide applications in fluorescent probe, biology imaging, light-emitting materials, etc. Biologically active oxygen hypochlorite (HClO) exists widely in the biological and chemical environment, which can pose a great threat to human health. Design of HClO-sensitive molecules in solvents is very important. Recently, Wu et al. [Wu L L, Yang Q Y, Liu L Y, et al.
2018 Chem. Commun. 54 8522 ] designed an ESIPT-based HBT-OMe probe molecule, which can detect HClO due to its methoxy-hydroxy-benzothiazole. They found that the fluorescence intensity of the system gradually increases with HClO increasing. However, the microscopic mechanism of this highly efficient fluorescent probe is not well understood. Therefore, in this work, we theoretically investigate the ESIPT mechanism of the HBT-Ome and its product molecule by using density functional theory and time-dependent density functional theory. Based on polarizable continuum model (PCM) with the integral equation formalism variant (IEFPCM) and Becke’s three-parameter hybrid exchange function with the Lee-Yang-Parr gradient-corrected functional (B3LYP) as well as the TZVP basis, the optimized structures are obtained. The structures show that the HBT-Ome product molecules tend to undergo proton transfer in the excited state but HBT-OMe molecules cannot undergo the proton transfer process. The analysis of frontier molecular orbitals not only explains the reason why the fluorescence of the HBT-Ome product is enhanced, but also demonstrates that the HBT-Ome fluorescence intensity is diminished owing to twisted intramolecular charge transfer in the excited state. It is twisted intramolecular charge transfer that leads smaller charge density to be overlapped and the fluorescence intensity of HBT-OMe molecule to be further weakened. Infrared vibrational spectrum shows the enhancement of intramolecular hydrogen bond of O—H, which indicates the tendency of proton transfer. The molecular covalent interaction analysis shows that the intramolecular interactions of HBT-OMe remain largely unchanged clearly. The intramolecular O—H bonding interaction is weakened, and the N—H bonding interaction is increased for HBT-OMe product molecule. The enhancement of intramolecular hydrogen bond of N—H further illustrates the trend of proton transfer. The calculated potential energy curve provides direct evidence for the occurrence of ESIPT in the HBT-Ome product molecule. Our work is of great significance in designing and synthesizing the HClO fluorescent probes based on ESIPT molecules.-
Keywords:
- excited-state intramolecular proton transfer /
- time dependent density functional theory /
- HClO
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图 1 优化的HBT-OMe-OMe几何构型 (a) S0态; (b) S1态. 产物分子几何构型 (c) S0态; (d) S1态. 其中粉色为氧原子, 绿色为氮原子, 黄色为硫原子
Fig. 1. Optimized structures of HBT-OMe: (a) S0; (b) S1. Product molecule: (c) S0; (d) S1. O atom: pink; N atom: green; S atom: yellow.
图 2 HBT-OMe的前线分子轨道 (a) HOMO; (b) LUMO. 产物分子的前线分子轨道 (c) HOMO; (d) LUMO
Fig. 2. The frontier molecular orbital of HBT-OMe: (a) HOMO; (b) LUMO. Product molecule: (c) HOMO; (d) LUMO.
图 4 HBT-OMe分子及产物分子在S0态((a), (c)), S1态((b), (d))的非共价相互作用图
Fig. 4. The RDG and scatter diagram of HBT-OMe and product molecule in S0 ((a), (c)) and S1 ((b), (d)).
表 1 HBT-OMe-OMe重要的二面角信息
Table 1. Dihedral angle information of HBT-OMe.
反应物 N1—C2—C3— C4 C3—C4—O5—C6 S0 26.247 3.223 S1 –101.690 –76.981 产物 N1—C2—C3—C4 C3—C4—O5—H6 S0 –0.005 –0.004 S1 0.028 –0.011 
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表 2 HBT-OMe的垂直激发能
Table 2. Vertical excitation energy of HBT-OMe.
Electronic excitation energy/nm Oscillator strengths Orbital transition 反应物 S1 392.86 0.0082 H → L (98.8%) S2 367.89 0.0003 H-1 → L (99.1%) 产物 S1 357.49 0.1228 H → L (96.9%) S2 307.23 0.4634 H-2 → L (4.3%)
H-1 → L (91.9%)
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[1] Chen K Y, Cheng Y M, Lai C H, Hsu C C, Ho M L, Lee G H, Chou P T 2007 J. Am. Chem. Soc. 129 4534
Google Scholar
[2] Coe J D, Martinez T J 2005 J. Am. Chem. Soc. 127 4560
Google Scholar
[3] English D S, Zhang W, Kraus G A, Petrich J W 1997 J. Am. Chem. Soc. 119 2980
Google Scholar
[4] Fischer M, Wan P 1998 J. Am. Chem. Soc. 120 2680
Google Scholar
[5] Fischer M, Wan P 1999 J. Am. Chem. Soc. 121 4555
Google Scholar
[6] Weller A 1956 Berichte der Bunsengesellschaft für physikalische Chemie 60 1144
[7] Keck J, Kramer H E A, Port H, Hirschk T, Fischer P, Rytz G 1996 J. Phys. Chem. 100 14468
Google Scholar
[8] Demchenko A, Klymchenko A, Pivovarenko V, Ercelen S, Duportail G, Mely Y 2003 J. Fluoresc. 13 291
Google Scholar
[9] Park S, Kwon J E, Kim S H, Seo J, Chung K, Park S Y, Jang D J, Medina B M, Gierschner J 2009 J. Am. Chem. Soc. 131 14043
Google Scholar
[10] Han J, Li Y Y, Wang Y, Bao X, Wang L, Ren L, Ni L, Li C 2018 Sens. Actuators B 273 778
Google Scholar
[11] Wu S M, Pizzo S V 2001 Arch. Biochem. Biophys. 391 119
Google Scholar
[12] Khatib S, Musa R, Vaya J 2007 Bioorg. Med. Chem. 15 3661
Google Scholar
[13] Mao L C, Liu Y Z, Yang S J, Li Y X, Zhang X Y, Wei Y 2019 Dyes Pigments 162 611
Google Scholar
[14] Dickinson B C, Chang C J 2008 J. Am. Chem. Soc. 130 11561
Google Scholar
[15] He Y H, Xu Y, Shang Y T, Zheng S W, Chen W H, Pang Y 2018 Anal. Bioanal. Chem. 410 7007
Google Scholar
[16] Pan Y M, Huang J, Han Y F 2017 Tetrahedron Lett. 58 1301
Google Scholar
[17] Wu L L, Yang Q Y, Liu L Y, Sedgwick A C, Cresswell A J, Bull S D, Huang C S, James T D 2018 Chem. Commun. 54 8522
Google Scholar
[18] Becke A D 1993 J. Chem. Phys. 98 5648
Google Scholar
[19] Zhu L X, Zhou Q, Cao B F, Li B, Wang Z R, Zhang X L, Yin H, Shi Y 2022 J. Mol. Liq. 347 118365
Google Scholar
[20] Arshad M N, Khalid M, Asad M, Braga A A C, Asiri A M, Alotaibi M M 2022 ACS. Omega. 7 11631
Google Scholar
[21] Yang D P, Yang G, Zhao J F, Zheng R, Wang Y S 2017 RSC Adv. 7 1299
Google Scholar
[22] Yang D P, Zhao J F, Zheng R, Wang Y S, Lyu J 2015 Spectrochim. Acta A 151 368
Google Scholar
[23] Zhao J F, Dong H, Yang H, Zheng Y J 2018 Org. Chem. Front. 5 2710
Google Scholar
[24] Zadeh S S, Ebrahimi A, Shahraki A 2023 Spectrochim. Acta Part A 292 122453
Google Scholar
[25] Song P, Li Y Z, Ma F C, Pullerits T, Sun M T 2013 J. Phys. Chem. C 117 15879
Google Scholar
[26] Zhou Q, Du C, Yang L, Zhao M Y, Dai Y M, Song P 2017 J. Phys. Chem. A 121 4645
Google Scholar
[27] Han J H, Liu X C, Li H, Yin H, Zhao H F, Ma L N, Song Y D, Y Shi 2018 Phys. Chem. Chem. Phys. 20 26259
Google Scholar
[28] Zutterman F, Liégeois V, Champagne B 2022 J. Phys. Chem. B 126 3414
Google Scholar
[29] Cammi R, Tomasi J 1995 J. Comput. Chem. 16 1449
Google Scholar
[30] Mennucci B, Cancès E, Tomasi J 1997 J. Phys. Chem. B 101 10506
Google Scholar
[31] Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 09, Gaussian, Inc, Wallingford, CT, USA, 2009
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Google Scholar
[33] Zhao G J, Han K L 2007 J. Phys. Chem. A 111 9218
Google Scholar
[34] Zhao G J, Han K L 2007 J. Phys. Chem. A 111 2469
Google Scholar
[35] Yang Y G, Liu Y F, Yang D P, Li H, Jiang K, Sun J F 2015 Phys. Chem. Chem. Phys. 17 32132
Google Scholar
[36] Yang Y J, Liu Y F, Yang D P, Li H, Jiang K, Sun J F 2015 Spectrochim. Acta Part A 151 814
Google Scholar
[37] Johnson E R, Keinan S, Mori-Sanchez P, Contreras-García J, Cohen A J, Yang W 2010 J. Am. Chem. Soc. 132 6498
Google Scholar
[38] Liu S L, Zhao Y S, Zhang C P, Lin L Q, Li Y X, Song Y F 2019 Spectrochim. Acta, Part A 219 164
Google Scholar
[39] Lu T, Chen F W 2012 J. Comp. Chem. 33 580
Google Scholar
[40] Humphery W, Dalke A, Schulten K 1996 J. Mol. Graph 14 33
Google Scholar
[41] Sobolewski A L, Domcke W 1999 J. Phys. Chem. A 103 4494
Google Scholar
[42] Sobolewski A L, Domcke W 1999 Phys. Chem. Chem. Phys. 1 3065
Google Scholar
[43] Li C Z, Ma C, Li D L, Liu Y F 2016 J. Lumin. 172 29
Google Scholar
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