Studies On The Syntheses And Properties Of Porphyrin-porphyrinoid Arrays By Metal-template Method

Porphyrin arrays have been actively explored due to its excellent photophysical properties and potential applications in optoelectronic devices,sensors,nonlinear optical materials and photodynamic therapy.The strongπ-electron interaction between porphyrin arrays makes them exhibit different properties with porphyrin monomers.The reported porphyrin arrays were usually arrays connected with porphyrins,or arrays connected with porphyrinoids and porphyrinoids.There were relatively few reports on porphyrin and porphyrinoid arrays.In addition,the metal-template method has been used to synthesize porphyrinoid monomer,and the research on the synthesis of porphyrin array was rare.In this paper,a series of porphyrin and norcorrole,5,10-diazaporphyrin,10-thiacorrole and other porphyrinoid arrays were synthesized by metal-template method.Their structures were characterized by X-ray single crystal diffraction and nuclear magnetic res onance spectroscopy.Their electrochemical and photophysical properties were also preliminarily studied by cyclic voltammetry(CV)and UV/vis absorption spectroscopy.The work of this paper is as follows:(1)Nickel porphyrin metal complexes were synthesiz ed by meso-formylation,pyrrole condensation,bromination,oxidation and metal coordination of two porphyrin monomers 1Ni and 2Ni.Then a series of meso-meso-linked porphyrin-norcorrole dimers and trimers were synthesized by metal-template method,and the intramolecular dimer product porphyrin-[32]octaphyrin arrays were also obtained.Some compounds were characterized by ~1H-NMR.In the single crystal structure of porphyrin-norcorrole trimer 21Ni and porphyrin-[32]octaphyrin array 22Ni,porphyrins were nearly orthogonal to the norcorrole or octaphyrin units.Compared with porphyrin monomer,the absorption peaks of porphyrin-norcorrole dimers,trimers and porphyrin-[32]octaphyrin arrays have a smaller red shift,ind icating that there is a weakπ-conjugated interaction between nickel porphyrin and norcorrole or octaphyrin compounds.(2)Porphyrin-BODIPY compound 24Ni was synthesized after meso-formylation,pyrrole condensation,bromination,oxidation and fluorboration of nickel porphyrin monomer 2Ni.Compound 24Ni was oxidized by ferric chloride,defluorinated boron unit with methyl sulfonic acid,and metal coordination to synthesize nickel porphyrin metal complex 27Ni.Then by metal-template method,compound 27Ni reacted with sodium azide to synthesize porphyrin-azaporphyrin-porphyrin fused array 30Ni;porphyrin-thiacorrole-porphyrin fused array 31Ni was synthesized by the reaction of27Ni with sodium sulfide nonahydrate.These compounds were characterized by~1H-NMR.The structures of compounds 27Ni and 30Ni were confirmed by X-ray single crystal diffraction.For the 30Ni and 31Ni fused arrays,their UV-Vis absorption spectra showed that compared with their respective porphyrinoid monomer and porphyrin monomer,the Q band had obvious red shift,extending to the near infrared(NIR)region.The electrochemical data show that 30Ni and 31Ni have smaller HOMO-LUMO gaps,which is consistent with the change of UV-visible absorption spectrum.The above information also shows tha t the fused porphyrin array formed by diazaporphyrin,thiacorrole and porphyrin extends theπ-conjugated system of porphyrin,and there is a strong electronic interaction between porphyrin and diazaporphyrin,thiacorrole.