1：Experimental Design and Method Selection:

The study involved synthesizing hetero-Pacman compounds (Re-TXP-Zn and Re-TXP-H2) by reacting TXP-Zn or TXP-H2 with Re(CO)5Cl in toluene. Characterization was done using UV-Vis spectroscopy, ESI-MS, elemental analysis, electrochemical methods, IR and 1H-NMR spectroscopy, and X-ray diffraction. Photocatalytic CO2 reduction experiments were conducted in DMF with sacrificial electron donors (TEA or TEOA/BIH) under CO2 atmosphere, using a 200 W Xenon lamp with various long-wave pass cutoff filters.

2：Sample Selection and Data Sources:

Compounds were synthesized and purified; solutions were prepared in DMF with specific concentrations (e.g., 5×10^-5 M catalyst).

3：List of Experimental Equipment and Materials:

Equipment included a Bruker DPX-300 or AV-400 spectrometer for NMR, Cary 100 or Agilent Cary 60 UV-Vis spectrometers, HORIBA Jobin Yvon IBH FluoroLog-311 spectrofluorimeter, Spitfire ACE laser system for transient absorption, potentiostat/galvanostat PGSTAT 101 for electrochemistry, and Shimadzu GC-17A gas chromatograph. Materials included silica gel, solvents (THF, toluene, DCM, DMF, MeOH), Re(CO)5Cl, TXP-Zn, TXP-H2, TEA, TEOA, BIH, and cutoff filters.

4：Experimental Procedures and Operational Workflow:

Synthesis involved heating reactants in toluene, purification by column chromatography, and recrystallization. Photocatalytic experiments involved bubbling CO2 through solutions, irradiation with filtered light, and sampling gas phase for CO analysis by GC.

5：Data Analysis Methods:

Data were analyzed using global fitting for transient absorption kinetics, calibration curves for GC quantification, and standard spectroscopic and electrochemical techniques.