一种具有非稠合氮杂环端基的A-D-A型分子的合成及性能研究

doi:10.6023/cjoc202409031

摘要/Abstract

在具有新型非稠合氮杂环端基苯基吡唑啉酮的苯环上进行了以氯为代表的端基修饰, 获得了一系列受体-供体-受体(A-D-A)型分子. 这种非稠合氮杂环端基分子苯基吡唑啉酮与经典的端基分子丙二腈茚二酮类相比, 具有合成步骤简单、成本低廉、环境友好等优势. 对合成的具有非稠合氮杂环端基的A-D-A型分子进行了相关性质的探究, 通过理论计算对合成的A-D-A型分子性质进行了预测, 并进行了紫外可见吸收、循环伏安曲线、X射线衍射和电子迁移率等测试, 表明了合成的A-D-A型分子的紫外可见吸收集中于波长500~700 nm区间, 具有接近1.7 eV的中等带隙. 同时通过对比探究了端基氯代对分子性质的影响, 这种非稠合氮杂环端基的受体分子被证明具有作为钙钛矿太阳能电池器件中的界面修饰层来修饰活性层的应用潜力.

关键词: A-D-A型分子, n型半导体, 非稠合端基, 中等带隙

Acceptor-donor-acceptor (A-D-A) type molecules, of which the novel non-fused azacyclic end-group pyrazolinones were modified with chlorine substitution on the phenyl ring, were synthesized. The non-fused azacyclic end-group pyrazolinones have the advantages of simple synthesis steps, low cost and environmental friendliness, compared to the classical end-group dicyanomethyleneindianone. The properties of the synthesized A-D-A type molecules with non-fused azacyclic end groups were characterized by theoretical calculation, UV-vis absorption, cyclic voltammetry, X-ray diffraction and space charge limited current. It is shown that the strong UV-vis absorptions of the synthesized A-D-A type molecules are located in the wavelength range of 500~700 nm, with a moderate band gap of nearly 1.7 eV. At the same time, the influence of end-group chlorination on the properties of A-D-A type molecules was compared and explored. It is proven that this kind of A-D-A type molecule with non-fused azacyclic end groups has the potential to be applied as interfacial modified layer of the active layer in perovskite solar cell devices.

Key words: A-D-A type molecule, n-type semiconductor, Non-fused end groups, Medium bandgap

引用此文

刘文睿, 音正春, 叶世棋, 徐智伟, 陈龙, 王官武. 一种具有非稠合氮杂环端基的A-D-A型分子的合成及性能研究[J]. 有机化学, 2025, 45(4): 1325-1333.

Wenrui Liu, Zhengchun Yin, Shiqi Ye, Zhiwei Xu, Long Chen, Guanwu Wang. Synthesis and Properties of Novel A-D-A Type Molecules with Non-Fused Azacyclic End Groups[J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1325-1333.

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图/表 7

Figure 1. Structures and synthesis routes of IC2F in the previous work and PMPs in this work

Figure 2. Synthetic route and molecular structures of BTP-P (3a), BTP-pCP (3b) and BTP-mCP (3c)

Figure 3. (a) Energies and dipole moments for three possible configurations of BTP-P calculated at the B3LYP/6-31G(d) level; (b) Torsion energies of BTP-P with torsion angles ranging from 0° to 360° (calculated at the B3LYP/6-31G(d) level); (c) Energy levels for the LUMO & HOMO and ESP diagrams of BTP-P, BTP-pCP and BTP-mCP

Figure 4. (a) UV-vis spectra of BTP-P in CHCl3 solution and neat film; (b) UV-vis spectra of BTP-pCP in CHCl3 solution and neat film; (c) UV-vis spectra of BTP-mCP in CHCl3 solution and neat film

Figure 5. (a) HOMO/LUMO energy levels calculated from CV measurements; (b) UV-vis spectra of BTP-P, BTP-pCP and BTP-mCP in neat films.

Figure 6. (a) Device structure; (b) J-V curves of best optimized devices with A-D-A type molecular interfacial modified layer and control devices

Device		V_OC/V	J_SC/(mA•cm^－2)	FF/%	PCE/%
Control	Average ^a	1.136±0.005	21.28±0.37	71.96±0.90	17.39±0.35
Control	Best	1.135	21.43	73.19	17.81
BTP-P treated	Average ^a	1.139±0.003	20.82±0.17	74.07±0.21	17.57±0.20
BTP-P treated	Best	1.144	21.01	73.95	17.78
BTP-pCP treated	Average ^a	1.134±0.005	22.01±0.21	75.03±0.39	18.73±0.27
BTP-pCP treated	Best	1.140	22.34	74.80	19.06
BTP-mCP treated	Average ^a	1.127±0.007	21.70±0.37	75.52±0.53	18.46±0.30
BTP-mCP treated	Best	1.123	22.18	76.06	18.95

Table 1. Device parameters with BTP-P (3a), BTP-pCP (3b) and BTP-mCP (3c) as interface modification layer

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