Design,Svntheses And Applications Of Metalloporphyrinic Framework Materials

It has been a hot topic in chemistry to construct new kinds of porous materials via self-assembling processes through covalent bonds, coordination bonds or other weak interactions. Scientists have elaborated in the rational designs and syntheses of porous materials for many years. Recently, two types of organic-framework materials MOFs (metal-organic frameworks) and COFs (covalent-organic frameworks) came into sight. Organic frameworks are crystalline and stable substances, with variable configurations and structural features for a number of applications.It’s of vital importance to choose organic ligands in MOFs’ or COFs’designs for specific constructions or usages. Explorations of porphyrinic materials are active fields, as they are possible candidates in versatile application fields, such as anti-cancer drugs, catalysis, semi-conductors, superconductors, electronic materials. NMR image enhancement reagent, NLO materials and DNA-bonding or cleavage reagent. Moreover, metal porphyrins have great chemical and thermal stabilities, and easily tailored with functional properties. All the characters mentioned above make metal-porphyrins be attractive building blocks for the assembly of nano-materials.In this thesis, we have synthesized four metalloporphyrinic ligands, M-TPyP, M-H4TCPP, H2TAPP and M-TEPP, to construct18porphyrinic MOF and COF materials. The framework structures were analyzed and confirmed by the experimental methods, such as X-ray single crystal diffraction, powder X-ray diffraction, FT-IR, TGA, EA, SEM, TEM, solid NMR and XPS etc. We have also explored the materials for their applications in fluroscence and catalysis. Brilliant catalytic effects were obtained especially in the fields such as olefin epoxidation, selective oxidation of alkylbenzenes and cyclohexane, and photo-oxidation of sulfide etc. Meanwhile, we also studied their heterogeneous nature, active catalytic sites and size effect of the catalysts.