摘要
合成了二茂铁修饰的卟啉与含有三氟甲基的卟啉.拉电子的三氟甲基使卟啉的紫外吸收发生蓝移,而给电子的二茂铁基则使卟啉的紫外吸收发生红移.在稳态荧光光谱中,二茂铁对卟啉荧光的猝灭程度大于三氟甲基,其中含有双二茂铁基的卟啉发生了66%的荧光猝灭,量子产率Φf仅为0.08,说明在激发态卟啉和二茂铁之间发生了较强的电子和能量的传递,这些结果在时间分辨荧光光谱研究中进一步被证实.电化学性质研究表明三氟甲基的引入使卟啉难失去电子,增加了卟啉的稳定性;二茂铁的给电子作用使卟啉更容易被氧化,是很好的电子给体.这些性质为此类化合物进一步应用于给受体体系的构筑提供了一定的理论依据.
Functionalized porphyrin and porphyrin containing trifluoromethyl with ferrocene were synthesized.The UV-Vis absorption bands of porphyrin with an electron withdrawing trifluoromethyl group were blue-shifted and those of porphyrin with an electron donating ferrocenyl group were red-shifted.The porphyrin containing ferrocenyl exhibited strong fluorescence quenching compared with those containing trifluoromethyl.The quenching efficiency of diferrocenyl porphyrin was about 66% with a quantum yield Φf of 0.08.These results indicated that there was a strong interaction between the excited state of porphyrin and ferrocene,which was further confirmed by the time-resolved fluorescence measurements.The electrochemical studies indicated that it was difficult to lost electron for the stable porphyrin with an electron withdrawing trifluoromethyl.However,the porphyrin with a ferrocenyl group was oxidized easily to lost electron and was a good electron donor.The re-search is supposed to provide some theoretical basis for this kind of compound using in donor-acceptor system.
引文
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