1：Experimental Design and Method Selection:

UV laser photolysis (193 and 266 nm) and thermal decomposition (flash vacuum pyrolysis at 600 K and 700 K) of sulfonyl azides CH2ClS(O)2N3 and CHCl2S(O)2N3 were used to generate nitrenes. Matrix-isolation IR and EPR spectroscopy in solid N2 (10 K) and glassy toluene (5 K) matrices were employed for characterization. Quantum chemical calculations at the B3LYP/6-311++G(3df,3pd) level supported the experimental findings.

2：Sample Selection and Data Sources:

Samples were prepared by reacting chloromethylsulfonyl chloride and dichloromethylsulfonyl chloride with sodium azide in acetonitrile. 15N-labeled samples were prepared using 1-15N sodium azide.

3：List of Experimental Equipment and Materials:

ArF excimer laser (193 nm), Nd3+:YAG laser (266 nm), UV lamp (365 nm), FT-IR spectrometer (Bruker 70 V), EPR spectrometer, glass vessels, cold U-traps, KBr beam splitter, MCT detector, Rh-plated copper block matrix support, aluminum oxide tube, tantalum wire, acetonitrile, sodium azide, chloromethylsulfonyl chloride, dichloromethylsulfonyl chloride, N2 gas, toluene.

4：Experimental Procedures and Operational Workflow:

Azides were synthesized and purified. Gas samples mixed with N2 were deposited onto a cold matrix support. Photolysis was performed with lasers and UV lamp. Pyrolysis was conducted using a heated tube. IR and EPR spectra were recorded before and after irradiations.

5：Data Analysis Methods:

IR spectra were analyzed for band positions and isotopic shifts. EPR spectra were used to determine zero-field splitting parameters. Quantum chemical calculations (DFT-B3LYP/6-311++G(3df,3pd)) were used for geometry optimizations, vibrational frequency analysis, and energy profile calculations.