Study On The Synthesis And Properties Of Directly Linked Porphyrin Arrays

?-conjugated porphyrin oligomers that possess characteristic delocalised electronic networks,have potential applications in models of artificial light-harvesting antenna complexes,for the most part,have been assembled by using alkene or alkyne type bridging units or by directly connecting individual porphyrin chromophores with multiple bonds to form fused porphyrin arrays.Porphyrin arrays have attracted particular attention due to their potential applications for nano-electronic devices,sensors,and soft materials possessing interesting nonlinear optical properties.Over the last two decades,extensive attention has been put on porphyrin arrays that bridged via a spacer.As a rare and extreme case,design and synthesis of directly linked porphyrin arrays is still a challenge in spite of some research on them.In the thesis,a series of ring-shaped or linear porphyrin oligomers that linked directly were synthesized for a further exploration of properties and structures of them.Based on the synthetic strategy of Suzuki-Miyaura reaction,cross-coupling between ?-borylated porphyrins and ?-bromoporphyrins successfully afford target molecules in a logical way.The key studies are listed below.(1)According to literature procedures,three kinds of porphyrin monomer were designed and synthesized:5,10-disubstitued porphyrin,5,15-disubstitued porphyrin and 5,10,15-trisubstitued porphyrin.?-borylporphyrins were obtained in a high yield via highly regioselective Ir-catalyzed ?-borylation of porphyrin oligomers.Bromination with N-bromosuccinimide and copper(?)bromide or treatment of porphyrin monomers with N-bromosuccinimide respectively afford P-brominated and meso-brominated porphyrins in a high yield.(2)A series of ?-? or meso-meso,?-? directly linked porphyrin oligomers were finally synthesized via the Pd-catalyzed Suzuki-Miyaura coupling of borylporphyrins and bromoporphyrins.(3)The structures of these directly linked porphyrin arrays were characterized by 1H NMR spectra and UV/vis absorption spetra and cyclic voltammetry were applied to examine their photophysical and electrochemical properties.