meso-四[(4-苯乙烯氨基)苯基]卟啉合成及其波谱特点  

Synthesis and Spectral Characters of meso-Tetra[4-(Benzylideneamino)phenyl] Porphyrin

作　　者：陈林[1] 佟珊玲[1] 吴雅红[1] 余坚[1] 阎雁[1] 

机构地区：[1]广东工业大学轻工化工学院,广州510006

出　　处：《应用化学》2013年第3期290-294,共5页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金资助项目(20771073)

摘　　要：以吡咯和对硝基苯甲醛为原料,经过环化、还原和缩合,合成了meso-四[(4-苯乙烯氨基)苯基]卟啉(TBAPP),通过UV-Vis、FT-IR、1H NMR及元素分析等对产物进行了表征,并对其荧光和电子顺磁共振特性进行了研究。卟啉产物的EPR测定显示出游离基特征,表明卟啉分子的大π共轭结构对周边基团产生的自由基有稳定作用。取代基对卟啉的紫外-可见吸收、光致发光及电子顺磁共振特性均有影响。四席夫碱苯基卟啉TBAPP的Q带比前体四氨基卟啉(TAPP)和母体四硝苯基卟啉(TNPP)红移,而Soret谱带变化较小;TBAPP的440 nm光激发的最大荧光峰658 nm分别比TAPP蓝移5 nm和比TNPP红移9 nm;TBAPP的EPR精细结构比TAPP弱,而比TNPP强。Using pyrrole and p-nitrobenzaldehyde as the starting materials, a novel conjugated product of meso- tetra [ 4- （ benzylideneamino ） phenyl ] porphyrin （ TBAPP ） was designed and synthesized after cyclization, reduction and condensation reactions. The product was characterized by UV-Vis, FT-IR, ＇H NMR determinations and elemental analysis. In addition, this porphyrin product was also investigated by fluorescence （FL） and electron paramagnetic resonance （EPR） methods. EPR measurement indicated that the prepared porphyrin molecule exhibited radical characteristics. The radicals were produced by the peripheral groups, which could be stabilized by the conjugated 7r-electrons of porphyrin molecule and detected under normal conditions. Meanwhile the substituent groups around the porphyrin ring contributed different influences on the spectral characters of UV-visible, fluorescence and electron paramagnetic resonance. Compare with its precursor of tetra-aminophenyl porpyrin（TAPP） and its parent compound of tetra-nitrophenyl porpyrin （TNPP）, Q bands of the Schiff base phenyl porphyrin TBAPP shifted towards red direction, while its Soret band kept changeless; meanwhile, under excitation at AEx =440 nm, its emission peak appeared at AEm =658 nm, with 5 nm and 9 nm blue shift than those of TAPP and TNPP; furthermore its EPR fine structure was weaker than TAPP and stronger than TNPP.

关 键 词：卟啉 席夫碱 电子顺磁共振 荧光光谱 

分 类 号：O621.2[理学—有机化学]