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

doi:10.6023/A23030071

Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (6): 613-619.DOI: 10.6023/A23030071 Previous Articles Next Articles

Article

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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Abstract

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

Cite this article

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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Fig. & Tab. 9

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

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

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

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

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)

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

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

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)

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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