Mechanism of fluorescence enhancement of HClO detected by excited-state intramolecular proton transfer based HBT-OMe molecule

Liu Xiao-Jun; Yang Xue

doi:10.7498/aps.72.20222313

Abstract

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

Authors and contacts

Liu Xiao-Jun¹,
Yang Xue²

1.
College of Science, Qiqihar University, Qiqihar 161006, China
2.
College of Science, Jilin Institute of Chemical Technology, Jilin 132022, China

Corresponding author: Liu Xiao-Jun, xiaojunliuqqhr@163.com

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11904126).

FullText HTML : translate this paragraph

References

[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
[32]	Wang Y, Shi Y, Cong L, Li H 2015 Spectrochim. Acta A 137 913 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

Cited By

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

Figure 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.

DownLoad: Full-Size Img PowerPoint

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

Figure 2. The frontier molecular orbital of HBT-OMe: (a) HOMO; (b) LUMO. Product molecule: (c) HOMO; (d) LUMO.

DownLoad: Full-Size Img PowerPoint

图 3 产物分子的IR振动光谱

Figure 3. The infrared vibrational spectrum of product molecule.

DownLoad: Full-Size Img PowerPoint

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

Figure 4. The RDG and scatter diagram of HBT-OMe and product molecule in S₀ ((a), (c)) and S₁ ((b), (d)).

DownLoad: Full-Size Img PowerPoint

图 5 产物的势能曲线

Figure 5. The potential energy curve of product molecule.

DownLoad: Full-Size Img PowerPoint

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

DownLoad: CSV

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%)

DownLoad: CSV

[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
[32]	Wang Y, Shi Y, Cong L, Li H 2015 Spectrochim. Acta A 137 913 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

[1]	Xing Feng-Zhu, Cui Jian-Po, Wang Yan-Zhao, Gu Jian-Zhong. Two-proton emission from excited states of proton-rich nuclei. Acta Physica Sinica, 2022, 71(6): 062301. doi: 10.7498/aps.71.20211839
[2]	Zhao Jia-Lin, Cheng Kai, Yu Xue-Ke, Zhao Ji-Jun, Su Yan. Theoretical research of time-dependent density functional on initiated photo-dissociation of some typical energetic materials at excited state. Acta Physica Sinica, 2021, 70(20): 203301. doi: 10.7498/aps.70.20210670
[3]	Li Ya-Sha, Sun Lin-Xiang, Zhou Xiao, Chen Kai, Wang Hui-Yao. Structure and excitation characteristics of C₅F₁₀O under external electric field based on density functional theory. Acta Physica Sinica, 2020, 69(1): 013101. doi: 10.7498/aps.69.20191455
[4]	Peng Jie, Zhang Si-Jie, Wang Ke, Dove Martin. Density functional theory calculation of spectrum and excitation properties of mer-Alq₃. Acta Physica Sinica, 2020, 69(2): 023101. doi: 10.7498/aps.69.20191453
[5]	Li Yuan-Yuan, Hu Zhu-Bin, Sun Hai-Tao, Sun Zhen-Rong. Density functional theory studies on the excited-state properties of Bilirubin molecule. Acta Physica Sinica, 2020, 69(16): 163101. doi: 10.7498/aps.69.20200518
[6]	Zhang Hong, Yin Hai-Feng, Zhang Kai-Biao, Lin Jia-He. Progress of surface plasmon research based on time-dependent density functional theory. Acta Physica Sinica, 2015, 64(7): 077303. doi: 10.7498/aps.64.077303
[7]	Xu Guo-Liang, Zhang Lin, Lu Zhan-Sheng, Liu Pei, Liu Yu-Fang. Electric field effects on the excited properties of Si2N2 molecule with special configuration：a density-functional study. Acta Physica Sinica, 2014, 63(10): 103101. doi: 10.7498/aps.63.103101
[8]	Hu Wen-Yong, Shao Yuan-Zhi. Anomalous diffusion in the formation of Turing pattern for the chlorine-iodine-malonic-acid system with a local concentration depended diffusivity. Acta Physica Sinica, 2014, 63(23): 238202. doi: 10.7498/aps.63.238202
[9]	Wang Zhi-Ping, Zhu Yun, Wu Ya-Min, Zhang Xiu-Mei. Time-dependent density functional theory studies of dynamics of hydroxy by proton impact. Acta Physica Sinica, 2014, 63(2): 023401. doi: 10.7498/aps.63.023401
[10]	Wang Zhi-Ping, Chen Jian, Wu Shou-Yu, Wu Ya-Min. Study of carbon atomic wire C5 in the laser field by time-dependent density functional theory. Acta Physica Sinica, 2013, 62(12): 123302. doi: 10.7498/aps.62.123302
[11]	Li Tao, Tang Yan-Lin, Ling Zhi-Gang, Li Yu-Peng, Long Zhen-Wen. Influence of external electric field on the molecular structure and electronic spectrum of paranitrochlorobenzene. Acta Physica Sinica, 2013, 62(10): 103103. doi: 10.7498/aps.62.103103
[12]	Zhang Lai-Bin, Ren Ting-Qi. Theoretical study of the ground and excited state properties of newly designed size-expanded adenine analogue x-adenine. Acta Physica Sinica, 2013, 62(10): 107102. doi: 10.7498/aps.62.107102
[13]	Cui Lei, Wang Xiao-Juan, Wang Fan, Zeng Xiang-Hua. Effect of laser polarization direction on high order harmonic generation of oxygen molecule——A simulation via TDDFT. Acta Physica Sinica, 2010, 59(1): 317-321. doi: 10.7498/aps.59.317
[14]	Zheng Jia-Jin, Lu Yun-Qing, Li Pei-Li. Optical nonlinearities of excited state intramolecular proton transfer molecule HBT. Acta Physica Sinica, 2010, 59(7): 4687-4693. doi: 10.7498/aps.59.4687
[15]	Zheng Jia-Jin, Lu Yun-Qing, Li Pei-Li, Chen Tao. All-optical switching effect of the excited state proton transfer molecule 2-(2'-hydroxyphenyl) benzothiazole in different polar solvents. Acta Physica Sinica, 2010, 59(9): 6626-6631. doi: 10.7498/aps.59.6626
[16]	Gu Bin, Cui Lei, Zeng Xiang-Hua, Zhang Feng-Shou. High-order harmonic generation of hydrogen molecule irradiated by ultra-strong femto-second laser pulse——a simulation via TDDFT. Acta Physica Sinica, 2006, 55(6): 2972-2976. doi: 10.7498/aps.55.2972
[17]	Cui Lei, Gu Bin, Teng Yu-Yong, Hu Yong-Jin, Zhao Jiang, Zeng Xiang-Hua. Effect of different laser polarization direction on high order harmonic generation of nitrogen molecule——A simulation via TDDFT. Acta Physica Sinica, 2006, 55(9): 4691-4694. doi: 10.7498/aps.55.4691
[18]	Cai Jian-Qiu, Tao Xiang-Ming, Chen Wen-Bin, Zhao Xin-Xin, Tan Ming-Qiu. Density functional theory study on the atomic structure and electronic states of Cu(100) (2×22)R45°-O surface. Acta Physica Sinica, 2005, 54(11): 5350-5355. doi: 10.7498/aps.54.5350
[19]	Gu Bin, Jin Nian-Qing, Wang Zhi-Ping, Zeng Xiang-Hua. Calculation of the transition spectra of sodium atom via TDDFT. Acta Physica Sinica, 2005, 54(10): 4648-4653. doi: 10.7498/aps.54.4648
[20]	LIANG XIAO-LING, LI JIA-MING. MINIMA OF OSCILLATOR STRENGTH DENSITIES FOR EXCITED ATOMS. Acta Physica Sinica, 1985, 34(11): 1479-1487. doi: 10.7498/aps.34.1479

Catalog

Vol. 72, Issue 11 - 2023-06-05

Metrics

Abstract views: 1945
PDF Downloads: 52
Cited By: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

Search

Article

留言板