Metal Oxo Cluster-based Porous Crystalline Framework Materials: Synthesis And Biomedical, Sensing, Lighting And Photocatalytic Properties

Metal oxo cluster-based framework materials(Metal-organic frameworks, MOFs) are a unique class of hybrid porous solids based on metals and organic linkers. Compared to traditional porous materials, they possess predominance of large surface areas, tunable pore size and shape, adjustable composition and functionalized pore surface, which enable them unique advantages and promises for applications in many areas including chemical separation, gas storage, catalysis, drug delivery and optical sensing/detection. With the rapid development in this field, thousands of MOFs with novel structures were synthesized and the researching center has transferred from studies of structures to development of multifunctional materials. More and more synthetic methods were proposed making rationally design and synthesis of MOFs material with special properties for unique applications possible.The largely increased number of novel MOFs materials provide lots of available materials for exploring their applications. Although MOFs materials have demonstrated excellent properties in many areas, there are still some important issues need to be further studied.In this dissertation, we design and synthesize two semi-rigid N-heterocyclic organic ligands with polycarboxyl groups as organic linker connecting d10 metal ions constructing four novel three-dimensional non-interpenetrated nanoporous MOFs materials with high porosity and investigation their properties in drug delivery, adsorption and separation of large cation, sensor of small moleculers, solid state fluorescence, solid state lighting, solid state phosphorescence, solid state two-phont adsorption, heterogeneous catalysis and so on. Studies this system based on the following considerations: I) Semi-rigid organic ligands not only possess a certain flexibility to generate various coordination geometries with metal ions but also have some degree of rigidity, being able to bring high porosity of MOFs materials; II) d10 metal ions could provide charge transfer with organic ligands which may generate luminescent properties to the whole frameworks; III) d10 metal ion, Zn2+, is compatible in vivo which will help us research the properties of MOFs materials for biological applications.1) By spontaneous resolution, a pair of 3D chiral non-interpenetrated nanoporous MOFs has been prepared from zinc ions and achiral TATAT ligands. Considering its high porosity, MOF1 has been used as materials for the adsorption and delivery of anticancer 5-fluorouracil and the experimental results indicate that it shows high drug loading(about 50% of the transported drug versus the carrier material) and slow release of the proportion of the loaded drug.[(CH3)2NH2]2[Zn(TATAT)2/3]·3DMF·H2O(MOF1)TATAT = 5,5’,5’’-(1,3,5-triazine-2,4,6-triyl)tris(azanediyl)triisophthalate2) Based on the special p H stability of ZIF-8, we have demonstrated, for the ?rst time, ZIFs material used as a p H-sensitive drug delivery vehicle. ZIF-8 shows a remarkable capacity of anticancer 5-FU, loading around 0.66 g of 5-FU g-1 of desolvated ZIF-8 and different drug release capability under acidic buffer solution(p H 5.0) and a neutral p H of 7.4.Zn(mim)2(ZIF-8)mim = 2-methylimidazolate3) Using size-extended hexatopic ligand TATAT and rod-shaped SBUs, left-handed 41 helical M-O-C(M=Zn, Na), we rationally constructed a non-interpenetrated MOFs with mesoporous channels. Owing to their high porosity and anionic frameworks of MOF1 and MOF2, the two porous compounds not only can be used for adsorption and separation of dye molecules but also exhibit selective adsorption and separation of cationic dyes that are quite different from the previously reported separation of MOFs based on size exclusion. Befiting from various available interaction sites of H bond, solvatochromic phenomena of MOF1 and MOF2 were observed on incorporating acetone and ethanol guests. Furthermore, MOF1 exhibited solvent-dependent photoluminescent intensity.[(CH3)2NH2]2[ZnNa2(μ2-H2O)2(H2O)2(TATAT)]·2DMF(MOF2)4) We introduce a strategy to achieve ef?cient white-light emission by encapsulating an iridium complex in the MOF cavity. A mesoporous blue-emitting MOF(MOF3) is prepared as host to encapsulate a yellow-emitting iridium complex, [Ir(ppy)2(bpy)]+. MOF3 was rationally designed and synthesized based on size-extended hexatopic ligand TATPT and Cd2+. The resultant composites emit bright white light with good colour quality, and high quantum yield up to 115 ℃. The white light-emitting-diode(WLED) assembly using an In Ga As N ultraviolet chip and this material can readily be fabricated.[(CH3)2NH2]15[(Cd2Cl)3(TATPT)4]·12DMF·18H2O(MOF3)2,4,6-tris(2,5-dicarboxylphenyl-amino)-1,3,5-triazine(TATPT)5) Modification of metal-organic frameworks(MOFs) with luminescent gold(III) complexes provides an entry to new phosphorescent materials having properties not easily accessed by the parental MOFs or gold(III) complexes. Cationic cyclometalated gold(III) complex through ion exchange incorporated into MOFs materials having anionic frameworks to form AuIII@MOFs. Through N2 sorption experiments of Au2@MOF2 with different content of Au2, SEM, EDX and ICP, we suggested that gold(III) complexes resided in the inner pores of the MOF host materials. In this work, strong phosphorescence with lifetime up to~50 μs in open air at room temperature has been achieved. The AuIII@MOFs display solid state two-photon-induced phosphorescence. Net reduction of methyl viologen to reduced radical(in the presence of Et3N) in air has been realized upon excitation at λ>370nm. This class of AuIII@MOFs has been shown to be reusable and size-selectiveheterogeneous photocatalysts for oxidative C–H functionalization reactions.[Me2NH2]2[(Cd2(TATMB)2]·10DMF·3H2O(MOF4)3,3’,3’-((1,3,5-triazine-2,4,6-triyl)tris(azanediyl))tribenzoic acid(H3TATMB)...