Synthesis and Properties of Novel A-D-A Type Molecules with Non-Fused Azacyclic End Groups

doi:10.6023/cjoc202409031

Abstract

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

Cite this article

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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Fig. & Tab. 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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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