Corrole Basicity in the Excited States: Insights on Structure–property Relationships
Journal of porphyrins and phthalocyanines(2020)
摘要
Steady-state fluorescence measurements and quantum-chemical DFT geometry optimizations are applied to extend the structure–property relationships between the free-base corrole macrocycle conformation and its basicity to the lowest excited S[Formula: see text] and T[Formula: see text] states. Direct basicity estimation in the lowest excited S[Formula: see text] state is demonstrated by means of fluorescence quantum yield measurements. The long wavelength T1 tautomer is found to retain its basicity in the S[Formula: see text] state, whereas the short wavelength T2 tautomer shows a noticeable decrease in basicity in the S[Formula: see text] state, which is related to the in-plane tilting of the pyrrole ring to be protonated. The conformational changes upon going from the ground to the lowest excited T[Formula: see text] state and the influence of the meso-aryl substitution pattern on the overall degree of distortions and tilting of the pyrrole ring to be protonated are also discussed from the point of view of macrocycle basicity.
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关键词
free-base corroles,NH tautomers,basicity,excited states,fluorescence,macrocycle distortions,pyrrole tilting
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