The Synthesis, Structure, and Optical Properties of Novel Rhodium(III) 12-Crown-4-porphyrinate in a Solution and a Polymer Film

Upon interaction of free-base 12-crown-4-substituted porphyrin with rhodium chloride trihydrate RhCl₃·3H₂O in benzonitrile, corresponding rhodium(III) crown-porphyrinate is obtained in a high yield. The structure of the obtained complex of rhodium(III) is determined based on the data of mass spectrometry, chemical analysis, electron absorption spectroscopy, and luminescence spectroscopy. An analysis of the luminescence properties of this compound in a DMSO–water solution and a polystyrene film is carried out. An analysis of the interaction of obtained rhodium(III) 12-crown-4-porphyrinate with sodium, potassium, and calcium cations in a solution is performed based on the data of electron absorption spectroscopy. The complex is not prone to self-association of the molecules in a DMSO–water solution and may be of interest as a photosensitizer for generation of singlet molecular oxygen. It is found that novel rhodium(III) crown-porphyrinate possesses fluorescence and phosphorescence properties in a polystyrene film and may be of interest as a luminescence temperature sensor by the ratio of the intensity of transitions of phosphorescence to fluorescence.