1：Experimental Design and Method Selection:

The study involved designing ligands with varying numbers of thiophene insertions into triphenylamine-based scaffolds, synthesizing corresponding MOFs, and evaluating their photoelectronic properties and photocatalytic performance in sulfonylation–cyclisation reactions. Theoretical models for photoredox catalysis and electrochemical measurements were employed.

2：Sample Selection and Data Sources:

Ligands H3MCTA, H3BCTA, and H3TCTA were synthesized and used to construct MOFs. Substrates included N-arylmethacrylamides and arylsulfonyl chlorides. Data were obtained from spectroscopic, electrochemical, and crystallographic analyses.

3：List of Experimental Equipment and Materials:

Equipment included NMR spectrometers (Bruker Avance 500 WB and 400 WB), elemental analyzer (Vario EL III), mass spectrometer (LC/Q-TOF Micromass), TGA instrument (Mettler-Toledo TGA/SDTA851), PXRD diffractometer (PANalytical Empyrean), FT-IR spectrometer (JASCO FT/IR-430), UV-vis spectrophotometers (Hitachi U-4100 and TU-1900), cyclic voltammetry setup, fluorescence spectrometer (Edinburgh FS920), and X-ray diffractometer (Bruker SMART APEX). Materials included organic solvents, chemicals like Zn(NO3)2·6H2O, DMF, HOAc, and substrates for reactions.

4：Experimental Procedures and Operational Workflow:

Ligands were synthesized via specific chemical reactions. MOFs were prepared solvothermally. Photocatalytic reactions were conducted in Pyrex tubes under visible light irradiation with a Xe lamp and UV cut-off filter, involving degassing, addition of reactants, and illumination. Products were isolated by chromatography.

5：Data Analysis Methods:

Data were analyzed using NMR, UV-vis, CV, fluorescence spectroscopy, TGA, PXRD, and single-crystal X-ray diffraction. Software included SAINT and SHELXL for crystallography, and standard curves for quantification.