1：Experimental Design and Method Selection:

The study involved synthesizing closo-carborane-appended luminophores and converting them to nido-carboranyl forms via deboronation with fluoride. Photophysical, electrochemical, and theoretical methods were used to characterize properties and mechanisms.

2：Sample Selection and Data Sources:

Samples included synthesized closo-OXD1–2, closo-DPS1–2, and their nido counterparts. Data were obtained from NMR spectroscopy, elemental analysis, X-ray crystallography, cyclic voltammetry, UV/Vis absorption, photoluminescence spectroscopy, and theoretical calculations.

3：List of Experimental Equipment and Materials:

Equipment included Bruker NMR spectrometer, elemental analyzer, melting point apparatus, Autolab/PGSTAT 101 system for cyclic voltammetry, Varian Cary 100 and HORIBA FluoroMax-4P spectrophotometers, Hamamatsu Quantaurus-QY C11347-11 for quantum yields, Edinburgh Instruments FS5 spectrophotometer for lifetime measurements, and Gaussian 16 for DFT calculations. Materials included decaborane, diethyl sulfide, n-tetrabutylammonium fluoride, THF, DMF, MeCN, and various chemicals for synthesis.

4：Experimental Procedures and Operational Workflow:

Synthesis involved reactions under nitrogen atmosphere, purification by column chromatography, and characterization. Photophysical measurements were done in THF solutions and PMMA films. Electrochemical studies used a three-electrode cell. Theoretical calculations optimized geometries and transitions using DFT and TD-DFT methods.

5：Data Analysis Methods:

Data were analyzed using NMR software, electrochemical analysis software, spectrophotometer software, and Gaussian 16 with AOMix for molecular orbital analysis.