1：Experimental Design and Method Selection:

The study involved the synthesis of three novel asymmetrical substituted phthalocyaninecobalt compounds with different bulky peripheral groups and their application as dopant-free hole-transporting materials in perovskite solar cells. The impact of these peripheral groups on the properties of the phthalocyanines was investigated.

2：Sample Selection and Data Sources:

The materials used included Co(OAc)2·4H2O, methyl 4-hydroxybenzoate, isoeugenol, butyl 4-hydroxybenzoate, 4-Nitrophthalonitrile, and 1,5-diazabicyclo[4.3.0] non-5-ene (DBU). The perovskite solar cells were fabricated with the structure of FTO/TiO2(compact)/TiO2(mesoporous)/Perovskite/HTM/Au.

3：0] non-5-ene (DBU). The perovskite solar cells were fabricated with the structure of FTO/TiO2(compact)/TiO2(mesoporous)/Perovskite/HTM/Au. List of Experimental Equipment and Materials:

3. List of Experimental Equipment and Materials: Instruments used included BIO-RADFIS3000 spectrophotometer, Varian 300 MHz spectrometer, MALDI-TOF, Nicoet Evolution 300 spectrophotometer, Fluorolog-Horiba fluoromet, Q500 thermo gravimetric analyse (TGA), Q20 differential scanning calorimeter (DSC), scanning electron micrograph (SEM, XL30S-FEG), Oriel solar simulator 91192, and Keithley 2400 Source meter.

4：Experimental Procedures and Operational Workflow:

The synthesis of the phthalocyanine compounds involved the cyclopolymerization of 4-aryloxy phthalonitrile, 4-nitrophthalonitrile, and Co(OAc)2·4H2O salt. The perovskite solar cells were fabricated by spin-coating the HTM on perovskite films.

5：Data Analysis Methods:

The optical properties were measured in dimethylformamide (DMF) solvent. The thermo properties were recorded using TGA and DSC. The photovoltaic performances were characterized by current voltage (J-V) measurements under simulated AM 1.5G solar irradiation at 100 mW·cm-2.