摘要： THE STEADY AND ULTRAFAST PHOTOPHYSICAL BEHAVIORS OF A SERIES OF PERIPHERALLY FLUROPHENYL SUBSTI... THE STEADY AND ULTRAFAST PHOTOPHYSICAL BEHAVIORS OF A SERIES OF PERIPHERALLY FLUROPHENYL SUBSTITUTED FREE BASE CORROLES F0C, F5C, F10C AND F15C HAVE BEEN INVESTIGATED. THE EFFECTS OF FLUROPHENYL PERIPHERAL SUBSTITUENTS ON THE ENERGIES OF THE FRONTIER MOLECULAR ORBITS (MOS) WERE ALSO STUDIED BY DFT CALCULATIONS. A BLUESHIFT INDUCED BY THE FLUROPHENYL GROUP WAS OBSERVED IN UV ABSORPTION AND FLUORESCENCE, WHICH IS CONSISTENT WITH AN INCREASE OF HOMO-LUMO ENERGY GAP (EHOMO-LUMO). IN ADDITION, THE FLUORINE SUBSTITUTION MAKES THE ENERGY DIFFERENCE BETWEEN HOMO (A2U) AND HOMO-1(A1U) SMALLER, THIS CAUSES A MORE MIXTURE OF 1(A2UEG) AND 1(A1UEG) CONFIGURATIONS OF F15C AS COMPARED TO F0C. THE FEMTOSECOND RESOLVED TRANSIENT ABSORPTION EXPERIMENT SHOWED AN ULTRAFAST RELAXATION FROM SORET TO Q BANDS (100FS) AND A VIBRATIONAL RELAXATION IN QX BANDS (2.15 PS). THE INFLUENCE OF THE ENERGIES CHANGING INDUCED BY FLUROPHENYL GROUPS ON FEMTOSECOND KINETICS CAN BE NEGLECTED, WHILE A CONSIDERABLE CHANGING OF THE INTERSYSTEM CROSSING AND THE T1 RELAXATION WAS OBSERVED AND THE MECHANISM IS ALSO DISCUSSED.显示全部
