meso-3,5-Bis(trifluoromethyl)phenyl-Substituted Expanded Porphyrins: Synthesis, Characterization, and Optical, Electrochemical, and Photophysical Properties
meso-3,5-Bis(trifluoromethyl)phenyl-Substituted Expanded Porphyrins: Synthesis, Characterization, and Optical, Electrochemical, and Photophysical Properties
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DOI：
10.1002/asia.200800229
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发表时间：
2008-01-01
影响因子：
4.1
通讯作者：
Imahori, Hiroshi
中科院分区：
文献类型：
--
作者：
Kang, Soonchul;Hayashi, Hironobu;Imahori, Hiroshi
在三氟乙酸催化下，3，5-二(三氟甲基)苯甲醛与缺电子的3，5-二(三氟甲基)苯甲醛发生缩合反应，意外地合成了一系列3，5-二(三氟甲基)苯基取代的膨化卟啉，包括[22][22]-[22]-稠合[22]-戊二烯-3，[26]-己烷-4，以及完整的[32]七氢呋喃-5与传统的5，10，15，20-tetrakis(3，5-bis(trifluoromethyl)phenyl)porphyrin-1。光学和电化学测量表明，随着共轭大环尺寸的增大，HOMO-LUMO能隙减小，并且与此趋势一致，激发单重态对基态的失活增强。
Trifluoroacetic acid-catalyzed condensation of pyrrole with electron-deficient and sterically hindered 3,5-bis(trifluoromethyl)benzaldehyde results in the unexpected production of a series of meso-3,5-bis(trifluoromethyl)phenyl- substituted expanded porphyrins including [22]sapphyrin 2, N-fused [22]pentaphyrin 3, [26]hexaphyrin 4, and intact [32]heptaphyrin 5 together with the conventional 5,10,15,20-tetrakis(3,5-bis(trifluoromethyl)phenyl)porphyrin 1. These expanded porphyrins are characterized by mass spectrometry, H-1 NMR spectroscopy, UV/Vis/NIR absorption spectroscopy, and fluorescence spectroscopy. The optical and electrochemical measurements reveal a decrease in the HOMO-LUMO gap with increasing size of the conjugated macrocycles, and in accordance with the trend, the deactivation of the excited singlet state to the ground state is enhanced.