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共价有机框架(COFs)材料是新型的晶态多孔聚合物材料。COF的组成和结构可以灵活定制，通过供体(D)-受体(A)共价键形成的COF可以排列成高度有序的网络结构，具有高效的电荷传输性能，是极具潜力的光电功能和非线性光学(NLO)材料。本文以常见的COF基元1,3,5-三(4-苯基)苯(TPB)、1,3,5-三(4-苯基)胺(TPA)、2,4,6-三(4-苯基)-1,3,5-三嗪(TPT)和1,3,5-三(4-联苯)胺(TBPA)组合而成的D-A型结构单元为研究对象，探究提升COF材料电荷传输性能和NLO性质的途径。采用密度泛函理论方法研究了TPB-TPA(1)和TPT-TPA(2)、TPB-TBPA(3)和TPT-TBPA(4)4种组成单元的结构、分子轨道、激发态跃迁特征和NLO性质。结果表明：含三嗪基的分子降低了HOMO和LUMO间的能级差以及低能吸收峰的跃迁能；另一方面，增加共轭链长度的同时有效降低了跃迁能，有效提升了体系电荷传输性能。化合物2和4的βtot值是化合物1和3的2倍以上，这说明三嗪基的加入非常有效地提升了体系NLO性质。另外，增长供体分子的共轭链使得体系第一超极化率降低，这是由于增长供体分子的共轭链虽然降低了低能激发态的跃迁能，但是同时减小了相应激发态的振子强度，从而使得体系第一超极化率降低。本文得到了有效提升COF材料NLO性质的途径：引入三嗪基提升受体的接受电子能力，同时排除了增长供体共轭链这种常用的手段，为实验上合成高性能COF材料提供了理论基础。
Abstract：Covalent organic framework(COFs) materials are new crystalline porous polymer materials.The composition and structure of COF can be flexibly customized, and the COF formed by the donor(D)-acceptor(A) covalent bond can be arranged into a highly ordered network structure, with efficient charge transport performance, and is a potential photoelectric function and nonlinear optics(NLO) material.In this paper, the D-A structural unit composed of common COF primitive 1,3,5-tri(4-phenyl) benzene(TPB),1,3,5-tri(4-phenyl) amine(TPA),2,4,6-tri(4-phenyl)-1,3,5-triazine(TPT) and 1,3,5-tri(4-biphenyl) amine(TBPA) was studied.To explore the way to improve the charge transport performance and NLO properties of COF materials.The structures, molecular orbitals, excited state transitions and NLO properties of TPB-TPA(1),TPT-TPA(2),TPB-TBPA(3) and TPT-TBPA(4) were studied by density functional theory.The results show that triazinyl molecules reduce the energy level difference between HOMO and LUMO and the transition energy of low energy absorption peaks.On the other hand, increasing the conjugated chain length effectively reduces the transition energy and effectively improves the charge transport performance of the system.The βtot values of compounds 2 and 4 are more than twice that of compounds 1 and 3,which indicates that the addition of triazinyl can effectively improve the NLO properties of the system.In addition, the increase of the conjugated chains of the donor molecules reduces the first hyperpolarizability of the system, because although the increase of the conjugated chains of the donor molecules reduces the transition energy of the low-energy excited state, it also reduces the oscillator strength of the corresponding excited state, thus reducing the first hyperpolarizability of the system.In this paper, a way to effectively improve the NLO properties of COF materials was obtained: triazinyl was introduced to improve the acceptor's electron ability, while the common means of increasing the conjugated chain of the donor was excluded, which provided a theoretical basis for the experimental synthesis of high-performance COF materials.
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基本信息:
DOI：10.20062/j.cnki.CN37-1453/N.2025.03.006
中图分类号:O641.4
引用信息:
[1]王丽.供体-受体共价有机骨架单元TPB、TPA、TPT和TBPA的非线性光学性质[J].鲁东大学学报(自然科学版),2025,41(03):254-260.DOI:10.20062/j.cnki.CN37-1453/N.2025.03.006.
基金信息:
国家自然科学基金(12304283); 山东省高等学校青创科技支持计划(2024KJG063)