Construction And Properties On Optical Functional Metal-organic Frameworks (MOFs)

The emergence of a new type of porous metal-organic framework (MOF) materials has significantly enriched the porous material domains, and porous MOFs been one of the most active endeavors among the inorganic and materials chemistry community. MOFs have shown promise in recognition, catalysis, separation, adsorption and magnetism and so on. Among them, there is an increasing trend in the exploration and discovery of functional luminescent MOFs. Their tunable pore size and characteristic functionality that are similar to active sites in proteins suggests they may act as bright promising host matrices for molecular recognition and catalysis, because the inherent confinement effect within their pores serves as preconcentrator to enhance the host-guest interactions and the pore surface designability enables the incorporation of appropriate specific catalytic sites into a scaffold through the use of strategic organic chemistry.This thesis mainly concerns on the construction and properity studies on the recognition and catalytic applications of luminescent MOFs with triphenylamine moiety as brigding ligands. Cu2+-based and Eu3+-based metal-organic framework realized the applications of MOFs in the luminescent detection of NO. The redox of paramagnetic characteristics of Cu2+ions with NO led to the change of fluorescence, and the material scaled down to the nanoregime can successfully been applied to biological imaging of NO in the living cells. Eu-MOF is a ratiometic probe for NO, greatly improving the sensitivity of the recognition process; Yb3+and Nd3+based MOFs realized the explosives recognition in NIR region, in which effective electron transfer from MOFs themself to electron-deficient nitroaromatic explosives quenches the MOF’s fluorescence; a multifunctional lanthanide-organic framework Tb-TCA that features a high concentration of Lewis-acidic Tb3+sites and Lewis-basic triphenylamine sites on its internal surfaces catalyzed both the Knoevenagel reaction and cyanosilylation in a size-selective fashion through base-type and acid-type catalysis sites, respectively. At the same time Tb-TCA realized in reasonably interpretating the activation process of the substrates in catalysis by ratiomatric fluorescence.In catalysis, firstly attempt to build chiral MOFs for asymmetric catalysis, by using proline derivatives as a chiral adduct, I perform the homochiral crystallization of the two enantiomorphs, having one-dimensional channels and coordinatively unsaturated metal sites, resepectively. Asymmetric cyanosilylations of aromatic aldehydes were dispalyed to validate the excellently enantioselective catalytic performance of the MOFs; Through incorporating the stereoselective organocatalyst and photosensitizer into a single framework, I have developed two enantiomeric MOFs to prompt the asymmetric a-alkylation of aliphatic aldehydes in a heterogeneous manner with high yield and high enantioselectivity. This is the first MOF-based heterogeneous catalyst for a-alkylation reaction using organic dyes as photocatalysts; Due to energy crisis and urgent demand for clean energy, a gadolinium-based porous MOF was assembled incorporating of4,4’,4"-nitrilotribenzoic acid as a photoactive building block for the encapsulation of proton reduction catalysts such as FeFe hydrogenase active site models and the tris(bipyridine)cobalt complex, prompting hydrogen production by light. Deposited the MOF to create membrane for light-driven hydrogen production suggested the huge potential for both fundamental understanding and practical applications.