In this work,we explore the excited states of three different[Ru(4,4’-BTFMB)_(2)(L)]^(2+)complexes(C1:L=bpy(2,2’-bipyridine);C2:L=phen(1,10-phenantroline);and C3:L=TAP(1,4,5,8-tetraazaphenanthrene)),aiming to invest...In this work,we explore the excited states of three different[Ru(4,4’-BTFMB)_(2)(L)]^(2+)complexes(C1:L=bpy(2,2’-bipyridine);C2:L=phen(1,10-phenantroline);and C3:L=TAP(1,4,5,8-tetraazaphenanthrene)),aiming to investigate the ligand effects on their photophysical and photochemical properties and also to evaluate their suitability as photosensitizers(PS)for photodynamic therapy(PDT).Compound C3 is a new theoretical proposition for which we have observed a significant lowering in the HOMO and LUMO energies,which can be interpreted as an extra stabilization of the complex,a highly desirable feature for a PS candidate.Also,the low-lying excited states showed a shift in the MLCT transition nature from dRu!π*btfmb to dRu!π*tap,confirming that the presence of a more electronegative atom in the third ligand lowers the energy of the orbitals due to a more effectiveπ-backbonding.Furthermore,the investigation of the excited state reactions has shown a dual character possibility for the three complexes,being thermodynamically favorable for photosensitizing molecular oxygen through energy transfer and oxidizing guanosine-monophosphate through electron transfer.Complex C3 presented the best reaction freeenergy profile,indicating that this new compound is most suitable for use as a photosensitizer in PDT.展开更多
文摘In this work,we explore the excited states of three different[Ru(4,4’-BTFMB)_(2)(L)]^(2+)complexes(C1:L=bpy(2,2’-bipyridine);C2:L=phen(1,10-phenantroline);and C3:L=TAP(1,4,5,8-tetraazaphenanthrene)),aiming to investigate the ligand effects on their photophysical and photochemical properties and also to evaluate their suitability as photosensitizers(PS)for photodynamic therapy(PDT).Compound C3 is a new theoretical proposition for which we have observed a significant lowering in the HOMO and LUMO energies,which can be interpreted as an extra stabilization of the complex,a highly desirable feature for a PS candidate.Also,the low-lying excited states showed a shift in the MLCT transition nature from dRu!π*btfmb to dRu!π*tap,confirming that the presence of a more electronegative atom in the third ligand lowers the energy of the orbitals due to a more effectiveπ-backbonding.Furthermore,the investigation of the excited state reactions has shown a dual character possibility for the three complexes,being thermodynamically favorable for photosensitizing molecular oxygen through energy transfer and oxidizing guanosine-monophosphate through electron transfer.Complex C3 presented the best reaction freeenergy profile,indicating that this new compound is most suitable for use as a photosensitizer in PDT.
