Study On Design,Synthesis,and Properties Of BODIPY-Porphyrin Hybrids

Since the structure and properties of LH1 and LH2 had been researched,many efforts have been devoted towards the synthesis of novel light harvesting materials.Among them,porphyrin derivatives and boron dipyrrin(BODIPY)are special dyes and fluorescence chromophores that have received much attention in light of their potential applications in modeling photosynthetic process,solar cells,chemsensors.Several reasons are listed to explain the future applications in light-harvesting materials about the combination of porphyrin and BODIPY.One one hand,porphyrin derivatives have good emission and absorption spectrum in the UV/vis region.However,the poor absorption in the blue-green region of 450-550 nm hinders its photophysical character.BODIPY have excellent absorption that can supplement porphyrin derivatives' absorption drawback in the corresponding visiable region.One the other hand,the low Stokes shift and reabsorption of BODIPY can also be adjusted by incorporating porphyrin chromophore into the conjugated system.Therefore,porphyrin and BODIPY are compatible system from a photochemical point of view.The combination of BODIPY and porphyrin will pave a new road to further research more novel optoelectrinic materials.In this thesis,a series of linear and cyclic BODIPY-porphyrin hybrids were sucessfully constructed by aldehyde condensation,oxidation,and then followed by complexation with BF3·Et2O.These compounds were fully characterized by 1H NMR,MALDI-TOF mass spectrum and X-ray crystal diffraction analysis futher confirm structures about some compunnds.The properties of the target compounds including photophysics,electrochemistry and host-guest chemistry have been investigated.The key studies are listed below:(1)According to literature,a-borylated pyrrole were synthesized via highly regioselective Ir-catalyzed C-H bond activation in high yields.Next,various pyrrole substituted porphyrins can be sufficiently obtained via Suzuki-Miyaura cross-coupling reaction between bromoporphyrins and a-borylation pyrrole.These pyrrole substituted porphyrins can smoothly proceed to condense with aromatic aldehydes and subsequent oxidation,and then complexation with BF3.Et2O can afford various BODIPY-porphyrin hybrids.We futher expanded this synyhetic method to construct phenylene bridged BODIPY-porphyrin hybrids and multiple BODIPY-porphyrin hybrids substituted porphyrins.(2)These BODIPY-porphyrin hybrids were characterized by 1H NMR,mass spectra and crystal diffraction analysis further confirm structures about some compounds.UV/vis absorption spectrum and electrochemical research suggest their these oligomers posses intriguing optoelectrinic properties,such as broad Q band that extended into infrared area and increasing HOMO-LUMO gaps with increasing phenylene BODIPY-porphyrin hybrids.UV/vis titration suggested BODIPY bridged Zn(II)porphyrin dimer can combine with DBACO in a 1:1 manner.