Studies On The Synthesis And Properties Of Azobenzene Bridged Porphyrin Arrays

In the last two decades, conjugated porphyrin arrays have been successfully utilized across a wide range of research disciplines and applications. Owing to numerous advantageous properties such as electronic, optical, electrochemical and magnetic propertie, porphyrin has been considered as promising candidates for future applications such as NIR dyes, photovoltaic dyes, nonlinear optical materials and nano-electronic device. In this paper, a series of azobenzene bridged porphyrin arrays and porphyrin-dipyrrin hybrids have been synthesized via Pd-catalyzed Suzuki-Miyaura cross-coupling reaction of β-borylated porphyrin, with p-brominated azobenzene or α-borylated dipyrrin. Further examination and discussion have been placed upon the photophysical, electrochemical properties, host-guest interaction and the isomerization processes of 12 M. The key studies are listed below:(1) According to literature procedures, Highly regioselective Ir/Pd-catalyzed β/meso-borylation porphyrins were synthesised in a high yields via 5,10,15-triarylporphyrin and 5,15-diarylporphyrin(aryl = 3,5-di-tert- butylphenyl) as the basic material. A series of cyclic β/meso azobenzene bridged porphyrin arrays were synthesized successfully through classic Pd-catalyzed Suzuki-Miyaura cross-coupling reaction of β/meso-borylated porphyrins with p-brominated azobenzene in a logical way. And the nanorings were characterized by 1H NMR spectra, mass spectra, X-ray single-crystal diffraction analysis and DFT caculations. The photophysical and electrochemical properties of these azobenzene bridged porphyrin arrays have been examined by UV/vis absorption spetra, fluorescence emission spectra and cyclic voltammetry.(2) A kind of new compounds which via azobenzene bridged between porphyrin and dipyrrin were synthesized through classic Pd-catalyzed Suzuki-Miyaura cross-coupling reaction of β-borylated porphyrin, p-brominated azobenzene and α-borylated dipyrrin. And these compound were characterized with 1H NMR, UV/Vis absorption, fluorescence spectra and single crystal X-ray diffraction analysis.