Design,Syntheses,and Properties Of Metal-Organic Framework Based On Sulfur-Aromatic Carboxylic Acid

First of all,it introduces the design and synthesis ofMOFmaterials,summarizes the characteristics and applications of MOF,and elaborates the background,significance and research content of this paper.In chapter 2,Reported herein is a planar tritopic carboxyl linker with secondary tripod donors sprouting off both sides at the core region.The merits extend beyond the interesting shape of the multiple tripod:e.g.,the two sets of sulfur tripods at the barrel region,together with the triazine center,offer a rich array of donors for adsorbing Hg(?)ions.The microporous solid also removes iodine from petroleum ether and water,and can be cycled in column chromatography.In chapter 3,Sulfur functionalization simultaneously mitigate the persistent instability issue of the famous Zr(?)-based MOF and impart effective metal uptake capabilities.One notable advance achieved pertains to a UiO-68-type porous solid featuring long-term stability in direct exposure to air,while maintaining significant mercury uptake capability from water and organic solutions.Also discovered is a cubic NU1100-type net that offers more efficient mercury removal capability than other thioether-equipped MOF materials.The maximum adsorption capacity is 322 mg/g.In chapter 4,the series of highly stable porous solids here feature systematic,regiospecific sulfur substitutions on the organic linkers for versatile functions.One major surprise lies in the controllable sequential reactions between sodium thiomethoxide(NaSMe)and octafluorobiphenyl-4,4'-dicarboxylic acid(8F).Namely,3,4,6 and 8 methylthio-substiltutions can be respectively achieved with regiospecificity.A second surprise lies in their persistent formation of the UiO-67-type net with Zr(?)ions.In addition to the remarkable breadth of functional control,all the Zr(?)-based crystalline solids here are stable in boiling water,in air as solventless,and under strongo oixdaiton conditions.In addition,thiolene has attracted extensive attention and research due to its rich and colorful chemical properties.However,thiolene are highly reactive,and there are still great challenges to construct porous metal-thiolene network solid materials.In chapter 5,a method for preparing thioester molecules as the masked form of the thiol linkers was proposed Through in-situ synthesis,a semiconducting and porous metal-dithiolene network in the highly ordered single crystalline state are assembledFinally,since thiolene have more abundant and active properties than thioethers,the introduction of thiolene into MOF is an important theme for the development of sulfur-functionalized MOF.In chapter 6,convenient synthetic methodologies of two thiol-functionized organic carboxylic acid ligands,H2L11 and H2L12,were discussed.Both ligands were firstly reported and contain rich thiol functional groups.