2, 3-二呋喃基马来酸酐光致分子开关机理研究

张树东; 王传航; 唐伟; 孙阳; 孙宁泽; 孙召玉; 徐慧

doi:10.7498/aps.70.20202039

摘要

基于第一性原理计算了2, 3-二呋喃基马来酸酐(2, 3-difurylmaleic anhydride, DFMA)的光致变色开关机理. 在获得DFMA分子开环(O-DFMA)和闭环(C-DFMA)稳定构型的基础上, 应用微动弹性带(NEB)法找到了开环与闭环之间的最小能量路径(MEP)及过渡态构型(TS-DFMA), 得出O-DFMA和C-DFMA的势垒分别是24959 cm^–1(3.0945 eV)和23328 cm^–1(2.8923 eV), 预示着DFMA分子可能为热稳定双稳态分子. 基于MEP曲线(基态S₀)对应的分子构型, 计算了DFMA最低8个单重激发态的势能曲线, 发现仅第1激发态(S₁态)在TS-DFMA构型时出现极小值. 结合分子轨道跃迁及其图像, DFMA分子光致变色的机理为: 1)闭环→开环: 在S₁–S₀共振跃迁的波长激光作用下, C-DFMA分子从S₀跃迁至S₁态, 然后分子沿S₁态势能曲线退激发, 在TS-DFMA构型处发生从S₁态到S₀态的交叉跳变回到O-DFMA构型, 完成由闭环→开环的开关动作. 这一开关过程中S₁态势能曲线单调下降, 预示着开环动作不会有荧光辐射发生; 2)开环→闭环: 在S₁–S₀共振跃迁的波长激光作用下, O-DFMA分子从S₀跃迁至S₁态. 从O-DFMA构型到TS-DFMA构型, S₁态势能曲线存在一段相对“平坦”的区域, 仅在接近TS-DFMA构型时才明显单调下降. 这意味着O-DFMA分子可能需要借助振动激发才能跨越S₁这段“平坦”区从而接近到TS-DFMA构型, 然后顺着单调下降的S₁态势能曲线退激发, 在TS-DFMA构型处发生从S₁态到S₀态的交叉跳变, 完成由开环→闭环的开关动作. 也正因为有起初S₁态势能曲线的平坦区, 这一激发开关过程中同时伴有荧光辐射发生. DFMA分子的光致变色机理预示着其适合制作荧光分子开关.

关键词:

Abstract

The photochromic switching mechanism of 2,3-difurylmaleic anhydride (DFMA) is investigated by first-principles calculations. Based on the stable structures of the open-ring (O-DFMA) and closed-ring (C-DFMA) of the DFMA, the minimum energy path (MEP) and the configuration of transition states (TS-DFMA) between the O-DFMA and C-DFMA are found by using the nudged elastic band (NEB) method, the potential barriers of O-DFMA and C-DFMA are 24959 cm^–1(3.0945 eV) and 23328 cm^–1(2.8923 eV), respectively, indicating that the DFMA molecule may be a thermally bistable molecule. Along the molecular configuration corresponding to the MEP curve (i.e. ground state S₀), the potential energy curves of the lowest 8 singlet excited states of DFMA are calculated. Among these energy curves, only the first electronic excited state (i.e. S₁ state) has a minimum value in the transition state (TS-DFMA) configuration. Combined with the molecular orbital transitions and orbital images, the photochromic mechanism of DFMA can be described as follows (1) From C-DFMA to O-DFMA process: under the action of the laser with S₁–S₀ resonance transition wavelength, the C-DFMA transits from S₀ to S₁ state, and then deactivates along the S₁ potential energy curve, until a cross jumping transition occurs at the TS-DFMA structure from S₁ to S₀ and finally the molecule along the S₀ potentioal energy curve returns to the O-DFMA configuration, then the switching action from closed-ring to open-ring is completed. The S₁ state potential energy curve drops monotonically in this switching process, implying that there will be no fluorescent radiation in this process. (2) From O-DFMA to C-DFMA process: under the action of the laser with S₁–S₀ resonance transition wavelength, O-DFMA transits from S₀ to S₁ state. From the O-DFMA to TS-DFMA structure, there is a relatively “flat” area in the potential energy curve of the S₁ state, and it decreases significantly only when it is close to the TS-DFMA. This means that O-DFMA needs to be excited with some vibrational modes to pass through the “flat” region of S₁ and approaching to the TS-DFMA configuration, and then DFMA de-excites from the S₁ state potential energy curve along a monotonic decline and a cross jumping transition from S₁ to S₀ occurs in the TS-DFMA configuration, completing the switching action from open-ring to closed-ring. It is also precisely because of the flat region of the potential energy curve of the initial S₁ state that this excitation and switching process is accompanied by fluorescent radiations. The photochromic mechanism of DFMA indicates that it is suitable for making fluorescent molecular switches.

Keywords:

作者及机构信息

曲阜师范大学物理工程学院, 曲阜　273165

通信作者: 张树东, zhangsd2@126.com

基金项目: 国家自然科学基金(批准号: 11705101)资助的课题

Authors and contacts

School of Physics and Physical Engineering, Qufu Normal University, Qufu 273165, China

Corresponding author: Zhang Shu-Dong, zhangsd2@126.com

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11705101)

文章全文 : translate this paragraph

参考文献

[1]	Irie M, Mohri M 1988 J. Org. Chem. 53 803 Google Scholar
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施引文献

图 1 光致变色机理示意图

Fig. 1. Schematic diagram of photochromic mechanism.

下载: 全尺寸图片幻灯片

图 2 DFMA分子的开环和闭环的稳态构型

Fig. 2. Steady-state structures of the open-ring and closed-ring of DFMA molecule.

下载: 全尺寸图片幻灯片

图 3 NEB法计算的开环/闭环之间的最小能量路径(MEP)

Fig. 3. Minimum energy path (MEP) between O-DFMA and C-DFMA calculated by NEB method.

下载: 全尺寸图片幻灯片

图 4 TD-DFT/B3LYP/def2-TZVP水平上计算的DFMA分子势能曲线

Fig. 4. DFMA molecular potential energy curves calculated with TD-DFT/B3LYP/def2-TZVP.

下载: 全尺寸图片幻灯片

图 5 S₀态到S₁态激发跃迁偶极矩平方随MEP的变化

Fig. 5. Square of the transition dipole moment from S₀ to S₁ state along the MEP.

下载: 全尺寸图片幻灯片

图 6 S₀态和S₁态势能曲线, 其中插图为HOMO和LUMO空间分布图

Fig. 6. Potential energy curves of S₀ state and S₁ state, where the inset is the spatial distribution diagram of HOMO and LUMO.

下载: 全尺寸图片幻灯片

图 7 ESD模拟的O-DFMA和C-DFMA吸收光谱

Fig. 7. O-DFMA and C-DFMA absorption spectra simulated by ESD.

下载: 全尺寸图片幻灯片

表 1 O-DFMA和C-DFMA分子稳态构型参数

Table 1. Stable state configuration parameters of O-DFMA and C-DFMA.

Methods	Structure	R_C2-C3/nm	R_O10-O17/nm	D_{O10-C2-C3-O17}/(°)	Total thermal energy (hartree)	Energy difference/cm^–1
BP/SVP	O-DFMA	0.1382	0.5552	20.24	–836.23050	1232
BP/SVP	C-DFMA	0.1450	0.3156	0.92	–836.22488	1232
B3LYP/TZVP	O-DFMA	0.1359	0.5482	21.33	–836.63680	1815
B3LYP/TZVP	C-DFMA	0.1447	0.3153	0.98	–836.62853	1815
B3LYP/def2-TZVP	O-DFMA	0.1359	0.5480	19.82	–836.68342	2055
B3LYP/def2-TZVP	C-DFMA	0.1445	0.3150	0.75	–836.67406	2055
NEB/def2-SVP	TS-DFMA	0.1380	0.3365	8.45

下载: 导出CSV

[1]	Irie M, Mohri M 1988 J. Org. Chem. 53 803 Google Scholar
[2]	Nakamura S, Irie M 1988 J. Org. Chem. 53 6136 Google Scholar
[3]	徐海兵, 何亭, 唐明静, 彭雪峰, 邓建国 2014 科学通报 59 2900 Google Scholar Hu H B, He T, Tang M J, Peng X F, Deng J G 2014 Chin. Sci. Bull. 59 2900 Google Scholar
[4]	Irie M, Uchida K 1998 Bull. Chem. Soc. Jpn. 71 985 Google Scholar
[5]	Tian H, Yang S 2004 Chem. Soc. Rev. 33 85 Google Scholar
[6]	齐国生, 肖家曦, 刘嵘, 蒋培军, 佘鹏, 徐端颐 2005 物理学报 53 1076 Qi G S, Xiao J X, Liu R, Jiang P J, She P, Xu D Y 2005 Acta Phys. Sin. 53 1076
[7]	孙峰, 刘然, 索雨晴, 牛乐乐, 傅焕俨, 季文芳, 李宗良 2019 物理学报 68 178502 Google Scholar Sun F, Liu R, Suo Y Q, Niu L L, Fu H Y, Ji W F, Li Z L 2019 Acta Phys. Sin. 68 178502 Google Scholar
[8]	Irie M 2000 Chem. Rev. 100 1685 Google Scholar
[9]	Feringa B L 2001 Molecular Switches (Germany: Wiley-VCH Verlag GmbH, Weinheim)
[10]	Tian H, Wang S 2007 Chem. Commun. 8 781
[11]	Zhang J, Zou Q, Tian H 2013 Adv. Mater. 25 378 Google Scholar
[12]	Patel P D, Mikhailov I A, Belfield K D 2009 Int. J. Quantum Chem. 109 3711 Google Scholar
[13]	Shoji H, Kobatake S 2013 Chem.Commun. 49 2362 Google Scholar
[14]	Mei X, Wang J, Zhou Z, Wu S, Huang L, Lin Z, Ling Q 2017 J. Mater. Chem. C 5 2135 Google Scholar
[15]	Uchida K, Nakayama Y, Irie M 1990 Bull. Chem. Soc. Jpn. 63 1311 Google Scholar
[16]	Nakayama Y, Hayashi K, Irie M 1990 J. Org. Chem. 55 2592 Google Scholar
[17]	Nakayama Y, Hayashi K, Irie M 1991 Bull. Chem. Soc. Jpn. 64 789 Google Scholar
[18]	郭妮, 李苑莹, 李亚珍, 刘峰毅 2019 中国科学化学 49 1289 Google Scholar Guo N, Li Y Y, Li Y Z, Liu F Y 2019 Sci. Sin. Chim. 49 1289 Google Scholar
[19]	Zakharov A V, Gaeva E B, Lvov A G, Metelitsa A V, Shirinian V Z 2017 J. Org. Chem. 82 8651 Google Scholar
[20]	Liu Y, Wang Q, Liu Y, Yang X Z 2003 Chem. Phys. Lett. 373 338 Google Scholar
[21]	Jacquemin D, Perpète E A 2006 Chem. Phys. Lett. 429 147 Google Scholar
[22]	Isegawa M, Morokuma K 2015 J. Phys. Chem. A 119 4191 Google Scholar
[23]	陈利菊, 姚保利, 韩俊鹤, 郜鹏, 陈懿, 王英利, 雷铭 2008 物理学报 57 5571 Google Scholar Chen L J, Yao B L, Han J H, Gao P, Chen Y, Wang Y L, Lei M 2008 Acta Phys. Sin. 57 5571 Google Scholar
[24]	Liu R, Bi J J, Xie Z, Yin K K, Wang D Y, Zhang G P, Xiang D, Wang C K, Li Z L 2018 Phys. Rev. Appl. 9 054023 Google Scholar
[25]	Li Z L, Bi J J, Liu R, Yi X H, Fu H Y, Sun F, Wei M Z, Wang C K 2017 Chin. Phys. B 26 098508 Google Scholar
[26]	Weigend F, Ahlrichs R 2005 Phys. Chem. Chem. Phys. 7 3297 Google Scholar
[27]	Mills G, J′onsson H, Schenter G 1995 Surf. Sci. 324 305 Google Scholar
[28]	Henkelman G, J′onsson H 2000 J. Chem. Phys. 113 9978 Google Scholar
[29]	de Souza B, Neese F, Izsák R 2018 J. Chem. Phys. 148 034104 Google Scholar
[30]	Neese F 2017 Comput. Mol. Sci. 8 e1327
[31]	Neese F, Wennmohs F, Becker U 2020 J. Chem. Phys. 152 224108 Google Scholar

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