一种基于芴的大环结构的有效降低内重组能的理论研究

doi:10.6023/A23030071

化学学报 ›› 2023, Vol. 81 ›› Issue (6): 613-619.DOI: 10.6023/A23030071 上一篇下一篇

研究论文

一种基于芴的大环结构的有效降低内重组能的理论研究

杨磊^a, 葛娇阳^a, 王访丽^a, 吴汪洋^a, 郑宗祥^a, 曹洪涛^a, 王洲^c, 冉雪芹^b^,^*(), 解令海^a^,^*()

a 南京邮电大学信息材料与纳米技术研究院/材料科学与工程学院有机电子与信息显示国家重点实验室南京 210023
b 南京工业大学柔性电子(未来技术)学院南京 211816
c 南京邮电大学计算机学院南京 210023

投稿日期:2023-03-06 发布日期:2023-05-19
基金资助:
中国博士后科学基金面上项目(2022M711684); 江苏省高等学校基础科学(自然科学)研究面上项目(22KJB430036); 国家自然科学基金(21503114); 国家自然科学基金(21774061); 国家自然科学基金(61605090); 国家自然科学基金(61604076); 南京邮电大学科学基金(NY215056); 南京邮电大学科学基金(NY214176); 南京邮电大学科学基金(NY215172); 南京邮电大学科学基金(2016XSG03)

A Theoretical Study on the Effective Reduction of Internal Reorganization Energy Based on the Macrocyclic Structure of Fluorene

Lei Yang^a, Jiaoyang Ge^a, Fangli Wang^a, Wangyang Wu^a, Zongxiang Zheng^a, Hongtao Cao^a, Zhou Wang^c, Xueqin Ran^b(), Linhai Xie^a()

a State Key Laboratory for Organic Electronics and Information Displays, Institute of Information Materials and Nanotechnology, College of Materials Science and Engineering, Nanjing University of Posts &Telecommunications, Nanjing 210023, China
b School of Flexible Electronics (Future Technologies), Nanjing Tech University (Nanjing Tech), Nanjing 211816, China
c College of Computer, Nanjing University of Posts and Telecommunications, Nanjing 210023, China

Received:2023-03-06 Published:2023-05-19
Contact: *E-mail: iamxqran@njtech.edu.cn; iamlhxie@njupt.edu.cn
Supported by:
China Postdoctoral Science Foundation(2022M711684); Natural Science Foundation of the Jiangsu Higher Education Institutions(22KJB430036); National Natural Science Foundation of China(21503114); National Natural Science Foundation of China(21774061); National Natural Science Foundation of China(61605090); National Natural Science Foundation of China(61604076); Nanjing University of Posts and Telecommunications Scientific Foundation NUPTSF, China(NY215056); Nanjing University of Posts and Telecommunications Scientific Foundation NUPTSF, China(NY214176); Nanjing University of Posts and Telecommunications Scientific Foundation NUPTSF, China(NY215172); Nanjing University of Posts and Telecommunications Scientific Foundation NUPTSF, China(2016XSG03)

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摘要/Abstract

有机半导体材料在有机发光二极管(OLED)、有机场效应晶体管(OFET)和有机太阳能电池(OSC)等领域应用广泛, 但有机半导体材料的迁移率较低, 不利于电子传输. 本工作基于芴分子设计并计算研究了具有“口”型结构的一类新型网格结构(OF), 与普通的大环分子相比, 它具有可以横向延伸的几何结构. 利用密度泛函理论研究了其分子结构, 环张力能和各种电子性质, 包括分子轨道、绝热电离势(IPa)、绝热电子亲和势(EAa)、重组能. 此外, 利用非共价相互作用和Normal Mode (NM)分析方法分别研究了分子内的弱相互作用和每个振动模式对OF重组能的贡献. 结果表明OF分子具有非常弱的环张力能(8.20 kJ/mol), 比较容易在实验室中合成. 通过分子内弱相互作用分析发现, 由于cis-OF横梁上的两个芴单元距离较近并且产生了一定的角度, 从而产生了π-π相互作用. 与Bis-Fl1, Bis-Fl2, Quarter-Fl1和Quarter-Fl2相比, OF分子的IPa降低, EAa提升, 证明了格子化效应能提高分子的空穴和电子注入能力. 同时, OF具有较低的IPa, 是一种非常具有潜力的p型分子材料. 另外, 当形成口字型芴格时, OF的空穴重组能和电子重组能都有所降低, 说明格子化效应是有效降低重组能的一种方式, 为未来设计具有优秀电荷传输性质的有机半导体材料提供了一种有效的策略.

关键词: 芴, 密度泛函理论, 弱相互作用, 重组能, 电荷传输

Organic semiconductor materials are widely used in organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), and organic solar cells (OSCs), but their low mobility is not conducive to electron transport. In this work, a novel class of grid structures based on fluorene (OF) with a “口” structure has been designed and calculated, which has a geometric structure that can extend laterally compared with ordinary macrocyclic molecules. Density functional theory was utilized to study its molecular structure, ring strain energy, and various electronic properties, including molecular orbitals, adiabatic ionization potential, adiabatic electron affinity potentials, and reorganization energies. In addition, the weak interactions within molecules and the contribution of each vibration mode to the reorganization energy of OF were investigated by using non-covalent interaction analysis and Normal Mode (NM) analysis, respectively. The results show that OF has a weak ring strain energy (8.20 kJ/mol) which will be easily synthesized. Through intramolecular weak interaction analysis, it is found that in cis-OF the two fluorene elements on the beam are close and produce a certain angle, the π-π interaction is generated. Compared with Bis-Fl1, Bis-Fl2, Quarter-Fl1 and Quarter-Fl2, the energy gap of OF molecules decreases, the highest occupied molecular orbital (HOMO) energy level increases, and the lowest unoccupied molecular orbital (LUMO) energy level decreases, corresponding to adiabatic ionization potential (IPa) and adiabatic electron affinity(EAa), that is, the IPa of OF molecules decreases and EAa increases, which proves that the lattice effect can improve the hole and electron injection ability of molecules. At the same time, OF has a lower IPa which would be a very potential p-type molecular material. Interestingly, the reorganization energy of both OF molecules decreased compared with BF and QF, indicating that the lattice effect is an effective way to reduce the hole and electron reorganization energy which provides a strategy for the design of organic semiconductor materials with excellent charge transport properties.

Key words: fluorine, density functional theory, weak interactions, reorganization energy, electron transport

引用此文

杨磊, 葛娇阳, 王访丽, 吴汪洋, 郑宗祥, 曹洪涛, 王洲, 冉雪芹, 解令海. 一种基于芴的大环结构的有效降低内重组能的理论研究[J]. 化学学报, 2023, 81(6): 613-619.

Lei Yang, Jiaoyang Ge, Fangli Wang, Wangyang Wu, Zongxiang Zheng, Hongtao Cao, Zhou Wang, Xueqin Ran, Linhai Xie. A Theoretical Study on the Effective Reduction of Internal Reorganization Energy Based on the Macrocyclic Structure of Fluorene[J]. Acta Chimica Sinica, 2023, 81(6): 613-619.

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图/表 9

图1. (a)分子设计图; (b) OF的分子图; (c)合成子BF1, BF2, QF1和QF2的分子图

Figure 1. (a) Schematic diagram of molecular design; (b) molecular diagram of OF; (c) molecular diagrams of BF1, BF2, QF1 and QF2

图2. 合成子BF1, BF2, QF1, QF2, cis-OF和trans-OF正视图和俯视图

Figure 2. Front and vertical views of BF1, BF2, QF1, QF2, cis-OF and trans-OF

分子名称	α	β
BF1		-84.50
BF2	37.33
QF1	-36.73, -36.98	-84.77
QF2	37.10	86.13, -85.65
cis-OF	-40.58, 40.58, -34.85, 34.85	-26.25, 26.25, 28.48, -28.48
trans-OF	88.76, 88.38, -88.76, -88.38	-35.60, 41.70, 35.60, -41.70

表1. 合成子BF1, BF2, QF1, QF2和cis-OF, trans-OF的二面角α, β的测量值

Table 1. Measurements of dihedral angles α and β for BF1, BF2, QF1, QF2, cis-OF and trans-OF

图3. 等键反应和同系异构反应的OF反应环应变能计算示意图

Figure 3. Schematic diagram of OF molecular ring strain energy calculation of isobond reactions and homodesmotic reaction

图4. BF1, BF2, QF1, QF2, cis-OF和trans-OF的电子云分布图以及HOMO-LUMO gap分布图

Figure 4. The frontier molecular orbitals (HOMO and LUMO) of the BF1, BF2, QF1, QF2, cis-OF, trans-OF as well as their relative energies and HOMO-LUMO gap (in eV)

图5. BF1, BF2, QF1, QF2, cis-OF和trans-OF的RDG函数对sign(λ2)ρ函数的散点图以及RDG填色等值面图, RDG等值面图根据sign(λ2)ρ在 -0.035 a.u.~0.02 a.u.范围内进行填色

Figure 5. The RDG functions of BF1, BF2, QF1, QF2, cis-OF and trans-OF are scatterplots of the sign (λ2)ρ function and the RDG fill isosurface plot, and the RDG isosurface plot is filled according to the range of sign (λ2)ρ in the range of -0.035 a.u.~0.02 a.u.

分子名称	λ(h)	IP_a	RMSD(VS+)	λ(e)	EA_a	RMSD(VS-)
BF1	0.146	6.856	0.104	0.177	-0.287	0.138
BF2	0.255	6.428	0.202	0.355	0.180	0.369
QF1	0.203	6.073	0.395	0.276	0.574	0.684
QF2	0.153	6.280	0.185	0.216	0.324	0.484
cis-OF	0.128	5.829	0.140	0.148	0.708	0.121
trans-OF	0.121	5.848	0.093	0.145	0.735	0.115

表2. 合成子BF1, BF2, QF1, QF2, cis-OF和trans-OF的空穴重组能λ(h), 电子重组能λ(e), 绝热电离能IPa, 绝热电子亲和势EAa, 中性态结构vs阳离子态的均方根偏差值RMSD(VS+), 中性态结构vs阴离子态的均方根偏差值RMSD(VS-)

Table 2. The internal reorganization energies (eV) calculated by AP method of BF1, BF2, QF1, QF2, cis-OF and trans-OF, as well as the IPa and EAa values; the root mean square displacement value RMSD (VS+) of neutral structure vs cationic state, and the value of RMSD (VS-) of neutral structure vs anion state

图6. cis-OF和trans-OF的振动模式对(a)空穴重组能λ(I)的贡献和(b)电子重组能λ(I)的贡献

Figure 6. The contribution of the vibration modes of cis-OF and trans-OF to (a) hole reorganization energy λ(I) and (b) electron reorganization energy λ(I)

图7. 四点法计算(a)空穴重组能和(b)电子重组能示意图

Figure 7. Schematic diagram of four-point method for (a) hole reorganization energy and (b) electron reorganization energy

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一种基于芴的大环结构的有效降低内重组能的理论研究

A Theoretical Study on the Effective Reduction of Internal Reorganization Energy Based on the Macrocyclic Structure of Fluorene

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