Elucidating J-Aggregation Effect in Boosting Singlet-Oxygen Evolution Using Zirconium-Porphyrin Frameworks: A Comprehensive Structural, Catalytic, and Spectroscopic Study

Metal-organic frameworks (MOFs) are powerful toolkits to directly correlate structure-function relationships due to their well-defined structures. In this work, 5,15-di(3,4,5-trihydroxyphenyl)porphyrin (DTPP) and 5,10,15,20-tetra(3,4,5-trihydroxyphenyl)porphyrin (TTPP) are reacted with zirconium ions to afford two MOFs (Zr-DTPP and Zr-TTPP) with acid and base tolerance in the pH range of 1.0-14.0. Powder X-ray diffraction investigation combined with Rietveld refinement reveals the J-aggregated porphyrin building blocks confined by benzene-1,2,3-trisolate-zirconium chains in the newly prepared Zr-DTPP. Electron spin-resonance, singlet-oxygen determination, and sulfides oxidation experiments demonstrate a much better singlet-oxygen evolution of J-aggregated Zr-DTPP than that of unaggregated Zr-TTPP reported previously, in good contrast to the weaker photocatalytic capability disclosed for DTPP than that for TTPP in solution, consummating the theory of photosensitizer J-aggregation in boosting heterogeneous photoinduced singlet-oxygen generation.