Controllable Synthesis And Property Of Metal-Organic Frameworks Based On The Rigid Heterocyclic Ligands

Due to the promising application in many areas, metal-organic frameworks have beenwidely investigated. With the development of synthesis chemistry, the center of research hastransfer from the construction of novel structures to the development of multifunction. It issignificant to design and synthesize MOFs with special properties. However, some importantissues still should be further studied, including the effect of framework charge distribution ongas adsorption, the effect of host/guest interaction on the properties of guest molecules,controllable synthesis, large scale preparation for practical production, improvement of gasadsorption, enhancement of framework stability, as well as catalyst uptake of porousmaterials.This work devotes to constructing some N-or S-containing MOFs by some rich-electronrigid heterocyclic ligands. The first aim is to studying the effect of reaction condition onresultants for achieving the controllable synthesis of MOFs. The second aim is to studying theeffect of substituent group on the properties of MOFs, including of gas adsorption, air/waterstability, for constructing of MOFs with high stability and excellent gas adsorption. The thirdaim is to studying the interaction of host and guest for preparing MOFs with special function.We achieve the controllable synthesis from the unexpected interpenetrating MOF（IFMC-27） to the predesigned non-interpenetrating MOF （IFMC-28） by changing the solventsizes. The S-containing MOF, IFMC-28, reveals the unusual Cu²⁺ion selective adsorptionfrom transition metal ions and succeeds in separating Cu²⁺and Co²⁺ions. To the best of ourknowledge, it is the first time that MOF-based materials are used in separating transitionmetal ions.Zn₄O（DMTDC）₃（DMF）₃·3DMF （IFMC-27）（DMTDC）₃·7DEF （IFMC-28）H2DMTDC:3,4-Dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acidTo further improve the stability of MOFs to air/water, the ligands containinghydrophobic group were taken into account. A hydrophobic S-containing MOF-5-like metalorganic framework has been synthesized. Due to the hydrophobic Ph-group, IFMC-29showsexcellent moisture resistance and water-stability. H2adsorption of IFMC-29has been studied.Zn₄O（MPTDC）₃·4DEF （IFMC-29）H2MPTDC:3-methyl-4-phenylthieno[2,3-b]thiophene-2,5-dicarboxylic acidNanoporous IFMC-8can be applied as the host materials for tuning the luminescenceproperty of Alq3chromophores. The different dispersion degree leads Alq3moleculesexhibiting the tunable luminescent emission from green light to blue light. More importantly,the excited-state lifetime of Alq3trapped in nanopore has been effectively prolonged. Theseresults might be helpful to fabricate the Alq3-MOFs composites. [Zn2（HBTT）Cl₂] CH3OH3DMA （IFMC-8）H3BTT:1,3,5-Tris（2H-tetrazol-5-yl）benzeneA novel polyoxometalate pillared compound （PMOF-1） based on the rarely recognised[Mo₆O₁₉]^4-units and a [Mo₆O₁₉]2–-templated metal-organic framework （PMOF-2） have beensuccessfully prepared. In PMOF-1, Six [Mo₆O₁₉]4–anions, twelve Ni²⁺metal ions and eightBIMB ligands construct a hydrophobic nanosize metal-organic cage. PMOF-1is a potentialsemiconductor with a wide band gap and promising catalyst for heterogeneous catalysis. InPMOF-2,[Mo₆O₁₉]2–anions sit inside the cavities of the metal-organic frameworks （MOFs）.It is a rare case of zinc phosphate/imidazole frameworks templated by polyoxometalate anions.PMOF-2is a potential heterogeneous catalyst.[Ni₂（BIMB）₂(Mo₄^VIMo₂^VO₁₉)]（PMOF-1）[Zn₄（BIMB）₄（PO₄）₂(Mo₆O₁₉)]·2H2O （PMOF-2）BIMB:1,4-bis（1-imidazolyl）benzene...