Zigzag-Shaped Donor-Acceptor Oligomers: Synthesis, Properties and Photovoltaic Applications

doi:10.6023/cjoc202505006

Abstract

Donor-acceptor (D-A) conjugated oligomers exhibit unique advantages in optoelectronic materials due to their well-defined molecular structures and ease of purification. However, current D-A oligomers incorporating electron-deficient units like benzothiadiazole (BTz) and naphthobisthiadiazole (NTz) are largely restricted to linear configurations. In this study, two novel D-A conjugated oligomers (VG1 and VG2) with zigzag-shaped topological structures were designed and synthesized by integrating the electron-donating indacenodithiophene (IDT) unit with the previously developed strong electron- withdrawing triphenylenobisthiadiazole (TPTz) unit. Due to the unique V-shaped structure of TPTz unit, VG2 demonstrates a slightly reduced bandgap by 0.04 eV as the number of repeating units increases, while its light absorption coefficient is significantly enhanced. When applied to organic photovoltaic devices, the VG2:Y6-based device achieves a power conversion efficiency (PCE) of 2.56%, outperforming the VG1:Y6 system (2.37%). This improvement is attributed to the reduced radiative recombination losses below the bandgap and lower non-radiative energy losses in the VG2:Y6 device. This work offers a new strategy for modulating the topological structure of conjugated oligomers and their optoelectronic properties.

Key words: donor-acceptor (D-A) structure, oligomers, organic solar cells, donor materials, structure-property-performance relationship

Cite this article

Yu Zhao, Ziyue Zhang, Shuwei Xu, Huawei Hu, Hongwei Wu, Linping Zhang, Fengkun Chen. Zigzag-Shaped Donor-Acceptor Oligomers: Synthesis, Properties and Photovoltaic Applications[J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4210-4219.

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Fig. & Tab. 6

Scheme 1. Synthetic route to the V-shaped oligomers

Figure 1. Optimized geometry and frontier molecular orbitals of (a) VG1 and (b) VG2 calculated at the B3LYP/6-31 G(d, p) level

Compd.	λ_solution^a/ nm	λ_film^a/ nm	λ_em^b/ nm	E_g^opt^c/ eV	E_HOMO^d/ eV	E_LUMO^d/ eV	Φ_FL-solid^f/ %	Φ_FL-solution^g/ %	τ_s^e/ns	k_r^h/ (10⁸ s^－1)	k_nr^h/ (10⁸ s^－1)
VG1	380, 457, 535	387, 469	647	2.05	－5.10	－3.09	0.8	45.3	4.3	1.05	1.27
VG2	383, 469, 515	389, 483, 572	650	2.01	－5.07	－3.09	1.8	41.3	3.4	1.21	1.72

Table 1. Optical and electrochemical data of VG1 and VG2

Figure 2. (a) Absorption spectra in DCM solution; (b) Films and (c) emission spectrum in DCM; (d) CV and DPV curves in DCM

Device	V_oc/V	J_sc/(mA•cm^－2)	FF/%	PCE/%	E_g/eV	ΔE₁/eV	ΔE₂/eV	ΔE₃/eV	E_loss/eV	EQE_EL/%
VG1:Y6	0.68	10.49	32.95	2.37	1.382	0.261	0.105	0.318	0.684	4.36×10^－4
VG2:Y6	0.78	10.44	31.33	2.56	1.371	0.260	0.035	0.298	0.592	9.78×10^－4

Table 2. Photovoltaic parameters of devices based on VG1 and VG2

Figure 3. (a) J-V curves of OSCs based on VG1 and VG2; (b) EQE spectra; (c) EQEEL curves of the corresponding OSC devices; (d) Jsc and (e) Voc against the light intensity of based on VG1 and VG2; (f) Summary of the detailed Eloss

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