Synthesis and characterizations of a paddlewheel-type dirhodium-based photoactive porous metal-organic framework

• A paddlewheel-type dirhodium-based MOF, [Rh2(ZnTCPP)], was prepared and characterized via synchrotron X-ray analyses.
• The porosity of [Rh2(ZnTCPP)] was confirmed via N2 adsorption isotherm measurement.
• The photophysical properties of [Rh2(ZnTCPP)] were investigated via diffuse reflectance UV-visble and emission spectra.

A paddlewheel-type dirhodium-based, photoactive, porous metal-organic framework, [Rh2(ZnTCPP)(H2O)7.5] ([1]; ZnTCPP = zinc tetra(4-carboxyphenyl)porphyrin), was prepared and characterized via synchrotron X-ray analyses (X-ray powder diffraction, extended X-ray absorption fine structure, and X-ray absorption near-edge structure), elemental analysis, infrared spectroscopy, and N2 gas adsorption isotherm analysis. Spectroscopic study revealed a drastic decrease in the emission intensity of [1] compared with [ZnTCPP], although features present in the absorption spectra of the two complexes were almost the same. This indicated that [1] underwent the photo-induced intramolecular charge transfer and/or energy transfer from the ZnTCPP moiety to dirhodium moiety.

A photoactive two-dimensional metal-organic framework constructed from paddlewheel-type dirhodium unit and zinc tetrakis(4-carboxyphenyl)porphyrin was synthesized and characterized via synchrotron X-ray analyses.Figure optionsDownload as PowerPoint slide