1：Experimental Design and Method Selection:

The study involved synthesizing a series of ruthenium polypyridyl complexes with ester- and amide-functionalized ligands to study halide supramolecular assembly in CH2Cl2. Methods included UV-Vis absorption, photoluminescence spectroscopy, NMR titrations, cyclic voltammetry, and time-resolved photoluminescence to characterize ground- and excited-state properties.

2：Methods included UV-Vis absorption, photoluminescence spectroscopy, NMR titrations, cyclic voltammetry, and time-resolved photoluminescence to characterize ground- and excited-state properties. Sample Selection and Data Sources:

2. Sample Selection and Data Sources: Samples were the synthesized ruthenium complexes (e.g., Ru-deaOH, Ru-dpaOH, Ru-dpa, Ru-daeaOH, Ru-da, Ru-deeb) and halide salts (TBA chloride and bromide) in CH2Cl2 solutions. Data were obtained from spectroscopic titrations and kinetic analyses.

3：List of Experimental Equipment and Materials:

Equipment included a Varian Cary 60 UV-Vis spectrophotometer, Horiba Fluorolog 3 fluorimeter, nitrogen dye laser system with PTI GL-301 dye laser and Hamamatsu R928 PMT, Bruker NMR spectrometers (400, 500, 600 MHz), BASi Epsilon potentiostat for electrochemistry, and microwave synthesizer (Anton Paar Monowave 300). Materials included ruthenium complexes, halide salts, solvents (CH2Cl2, CH3CN, etc.), and competitors like TBA triflate and TBA tetrafluoroborate.

4：0). Materials included ruthenium complexes, halide salts, solvents (CH2Cl2, CH3CN, etc.), and competitors like TBA triflate and TBA tetrafluoroborate. Experimental Procedures and Operational Workflow:

4. Experimental Procedures and Operational Workflow: Complexes were synthesized via microwave irradiation, purified, and characterized. Titrations with halides were performed in CH2Cl2, monitoring changes in UV-Vis and PL spectra. Competitive binding experiments were used for high Keq values. NMR titrations in CD2Cl2 tracked chemical shifts. Time-resolved PL and transient experiments measured excited-state kinetics.

5：Data Analysis Methods:

Data were analyzed using Benesi-Hildebrand analysis for equilibrium constants, square-scheme kinetic analysis for excited-state rate constants, and F?rster cycle for K*_eq. Software included Origin 2017 and Mathematica for fitting and calculations.