1：Experimental Design and Method Selection:

The synthesis involved a copper-catalyzed azide-alkyne cycloaddition (CuAAC) click reaction to form a macrocyclic crown ether. Various reaction conditions were tested, with the optimal using Cu(0), CuSO4·5H2O, and TBTA ligand. Characterization included NMR, FT-IR, mass spectrometry, X-ray crystallography, UV-Vis, and fluorescence spectroscopy.

2：Sample Selection and Data Sources:

Compounds were synthesized from commercial reagents, with starting materials prepared as described. Solvents were spectroscopic grade.

3：List of Experimental Equipment and Materials:

Equipment included NMR spectrometers (Bruker Avance III 300 MHz, Jeol ECS 400 MHz), FT-IR spectrometer (PerkinElmer Spectrum Two), mass spectrometer (Thermo Scientific LTQ Orbitrap XL), X-ray diffractometers (Xcalibur Atlas Gemini ultra, Diamond Light Source beamline I19), UV-Vis spectrophotometer (Shimadzu UV-1800), spectrofluorophotometer (Shimadzu RF-6000), and photoluminescence spectrometer (Edinburgh FLS980). Materials included copper powder, CuSO4·5H2O, TBTA, solvents (THF, DCM, MeCN, etc.), and hexafluorophosphate salts.

4：0). Materials included copper powder, CuSO4·5H2O, TBTA, solvents (THF, DCM, MeCN, etc.), and hexafluorophosphate salts. Experimental Procedures and Operational Workflow:

4. Experimental Procedures and Operational Workflow: Synthesis of CPYR involved reacting the diazide with the diacetylene derivative under N2 atmosphere, purification via preparative TLC, and crystallization. Coordination experiments involved adding salts to CPYR solutions and recording NMR, UV-Vis, and fluorescence spectra.

5：Data Analysis Methods:

NMR data were analyzed for chemical shifts, mass spectrometry for molecular weight confirmation, X-ray crystallography for structural determination using software like CrysAlisPro and Olex2, UV-Vis and fluorescence for spectral analysis, and DFT calculations for excited-state structures.