1387582-25-3Relevant academic research and scientific papers
Synthesis, structure, spectroscopic, and electrochemical properties of highly fluorescent phosphorus(V)-meso-triarylcorroles
Ghosh, Avijit,Ravikanth, Mangalampalli
, p. 6386 - 6396 (2012)
The synthesis, spectroscopic, and electrochemical properties of seven new PV-meso-triarylcorroles (1-7) are reported. Compounds 1-7 were prepared by heating the corresponding free-base corroles with POCl3 at reflux in pyridine. Hexacoordinate PV complexes of meso-triarylcorroles were isolated that contained two axial hydroxy groups, unlike the PV complex of 8,12-diethyl-2,3,7,13,17,18- hexamethylcorrole, which was pentacoordinate, or the PV complex of meso-tetraphenylporphyrin, which was hexacoordinate with two axial chloro groups. 1H and 31P NMR spectroscopy in CDCl3 indicated that the hexacoordinated PV-meso-triarylcorroles were prone to axial-ligand dissociation to form pentacoordinated PV-meso- triarylcorroles. However, in the presence of strongly coordinating solvents, such as CH3OH, THF, and DMSO, the PV-meso-triarylcorroles preferred to exist in a hexacoordinated geometry in which the corresponding solvent molecules acted as axial ligands. X-ray diffraction of two complexes confirmed the hexacoordination environment for PV-meso- triarylcorroles. Their absorption spectra in two coordinating solvents revealed that PV-meso-triarylcorroles showed a strong band at about 600 nm together with other bands, in contrast to PV-porphyrins, which showed weak bands in the visible region. These compounds were easier to oxidize and more difficult to reduce compared to PV-porphyrins. These compounds were brightly fluorescent, unlike the weakly fluorescent PV- porphyrins, and the quantum yields for selected PV-corroles were as high as AlIII and GaIII corroles, which are the best known fluorescent compounds among oligopyrrolic macrocycles. Copyright
