Design,Synthesis,and Properties Of Novel Expanded Porphyrin Based On BODIPY

Porphyrinoid have attracted extensively attention owing to their potential applications,such as magnetic resonance imaging?MRI?,dye-sensitized solar cells?DSSC?,organic semiconductors,photodynamic therapy?PDT?,nonlinear optics materials,ion recognition and models for aromaticity.As important members of porphyrinoid,expanded porphyrins have been widely investigated to reveal flexible conformation,rich metal coordination chemistry,versatile electronic states and extraordinary chemical reactivities.In this thesis,three types of expanded porphyrins?neo-confused smaragdyrin,orangarin and expanded azaporphyrin?were synthesized using?,??-dibromo BOIDPYs as starting materials.Related properties of these macrocyclic compounds have been detailed explored.The main investigations are listed below.1.Singly and doubly neo-confused[22]smaragdyrin-BF₂ complexes were furnished via S_NAr reaction of?,??-dibromo BODIPY with N-confused tripyrranes.The unique reactivity of these complexes were explored and a series of novel neo-confused smaragdyrin derivatives were prepared.Diprotonation behavior of singly and doubly neo-confused[22]smaragdyrins with methanesulfonic acid were discovered.X-ray diffraction analysis showed that singly and doubly neo-confused[22]smaragdyrins dicaiton species contained an interesting sp³ methylene segment in the neo-confused pyrrole unit.Comparing with regular[22]smaragdyrins-BF₂,reduced antiaromaticites,small HOMO-LUMOgap and red-shifted absorption spectra of neo-confused[22]smaragdyrins-BF₂ were observed.2.We developed a new method for preparing meso-aryl-substituted[20]orangarin-BF₂ complexes and[20]orangarin through S_NAr reaction of?,??-dibromo BODIPY with pyrrolyldipyrrin.Treatment of[20]orangarin with[Rh?CO?₂Cl]₂ resulted in facile metalation to give metal complex[20]orangarin-Rh?CO?₂.Approximate flat structures of[20]orangarin-BF₂complex and[20]orangarin were confirmed by X-ray diffraction analysis.The absorption spectra of[20]orangarin and its derivatives show remarkably near-infrared absorptions from 800 to 1600 nm.The antiaromaticity of[20]orangarins were demonstrated by NMR and DFT calculation.3.Key intermediate?-amino-??-bromo-BODIPY was prepared by S_NAr reaction of?,??-dibromo BODIPY with NH₃·H₂O.Azaoctaphyrin-?BF₂?₄,azadecaphyrin-?BF₂?₅ and azadodecaphyrin-?BF₂?₆were synthesized by Buchwald-Hartwig coupling reaction of?-amino-??-bromo-BODIPY.Azaoctaphyrin-?BF₂?₄K was obtained by treatment of azaoctaphyrin-?BF₂?₄ with K₂CO₃ in air.The optical,electrochemical properties of these expanded azaporphyrins were explored.X-ray diffraction analysis showed that azaoctaphyrin-?BF₂?₄ displayed a saddle-shaped structure and K⁺was tied in the center of macrocycle by non-covalent interactions with BF₂ moieties.Comparing with diazaporphyrin,the absorption spectrum of azaoctaphyrin-?BF₂?₄K shows a bathochromic shift Soret band and Q band,indicating its aromatic nature.