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用稳态和时间分辨光谱对四苯基卟啉、四甲基苯基卟啉、邻二氯苯基卟啉的锌、铜的络合物进行了表征.铜邻二氯苯基卟啉在极性溶剂中吸收光谱蓝移,并且产生一个新的电荷转移(CT)态的吸收带.CT态的荧光发射位于650nm,荧光寿命为8.4ns.反常荧光产生的原因是按照Marcus电子转移理论,极性溶剂有利于增加溶剂外部重组能,从而降低电子转移过程的活化能.此外,邻二氯苯基铜卟啉中的卤素原子的存在产生重原子效应,从而增加了其三线态的寿命.导致其三线态向CT态跃迁的几率变大.其他的影响因素如氢键、极性、轴配位的影响等因素被排除.
The complexes of tetraphenylporphyrin, tetramethylphenylporphyrin and ortho-dichlorophenylporphyrin were synthesized by means of steady-state and time-resolved spectroscopy. Copper orthodichlorophenyl porphyrin The absorption spectrum in the polar solvent is blue-shifted and a new charge-transfer (CT) absorption band is generated.The fluorescence emission in the CT state is at 650 nm and the fluorescence lifetime is 8.4 ns.The reason for the abnormal fluorescence is that according to Marcus electron transfer theory, Polar solvents help to increase the external recombination energy of solvents and reduce the activation energy of electron transfer.In addition, the presence of halogen atoms in o-dichlorophenyl copper porphyrin has a heavy atom effect, which increases the lifetime of the triplet state. Leading to a higher probability of its triplet transition to the CT state.Other factors such as hydrogen bonding, polarity and axial coordination are excluded.