1：Experimental Design and Method Selection:

The study involved the design and synthesis of two small molecular donors (TPA-DPP and TPA-DPP-MDN) with asymmetric push-pull structures. The methodology included thermogravimetric analysis, UV–vis spectra, X-ray diffraction, density functional theory (DFT) calculation, electrochemical and photovoltaic (PV) measurements.

2：Sample Selection and Data Sources:

The samples were synthesized using reagents purchased from Aldrich, Acros, and TCI Chemical Co. The solvents were further purified under nitrogen flow.

3：List of Experimental Equipment and Materials:

Equipment used included a Bruker DRX 400 spectrometer for 1H NMR spectra, Vario EL elemental analysis instrument, Thermo Scientific Q Exactive for HRMS, TGA 2050 for thermal stability, Shimadzu UV-1800 spectrometer for UV–vis absorption spectra, 970CRT fluorescence spectrophotometer for fluorescence spectra, CHI 600D electrochemical workstation for CV measurements, and PANalytical X’Pert PRO diffractometer for XRD.

4：Experimental Procedures and Operational Workflow:

The synthesis involved multiple steps including Suzuki coupling, bromination, and condensation reactions. The photovoltaic devices were fabricated with an architecture of ITO/PFN/SMDs:PC61BM/MoO3/Ag and characterized under AM 1.5 G irradiation.

5：5 G irradiation. Data Analysis Methods:

5. Data Analysis Methods: The data were analyzed using DFT calculations with PBE0/6-311G* basis set, and the photovoltaic parameters were determined from J-V characteristics and IPCE measurements.