Metal organic frameworks mofs are crystalline porous solids. Mechanically interlocked linkers inside metal organic. This dissertation focuses on studies of mechanically interlocked molecules mims specifically 2rotaxanes in three principle areas. Supramolecular organic frameworks containing metal rotaxane subunits rsofs hanyuan gong,a brett m. Letters hybrid organic inorganic rotaxanes and molecular shuttles chinfa lee1, david a. Metalorganic rotaxane frameworks assembly by cucurbit6. Metal organic framework mof materials have been prepared that contain a mechanically interlocked molecule mim as the pillaring strut between two periodic zncarboxylate layers. Coupled molecular switching processes in ordered mono.
The singlecrystal xray structures of mofs uwdm2 1,4diazophenyldicarboxylate. Mechanically interlocked linkers inside metalorganic. A series of metal organic framework mof materials has been prepared, each containing a mechanically interlocked molecule mim as the linker and a copperii paddlewheel as the secondary building unit sbu. The burgeoning field of metal organic frameworks or porous coordination polymers has received increasing interest in recent years. Rotors, motors, and machines inside metalorganic frameworks. Stoppering has been performed by reacting the resulting prerotaxane with the amino derivative of a zinc tetraarylporphyrin under edc. There are limitless applications for metal organic catenanes and rotaxanes in drug delivery, bactericide containing biomedical devices, electronic assemblies and molecular machines 2326. The mim linkers are 2rotaxanes with varying sizes of crown ether macrocycles 22crown6, 22c6. Metal ion directed metalorganic rotaxane frameworks with intrinsic features of selfpenetration and interpenetration jun liang,a xinlong wang,a yanqing jiao,a chao qin,a kuizhan shao,a zhongmin sua and qingyin wub ai n s ti ue of fc tia lmrche my,k l b p xo s en ry ed on ac y.
Pdf electrochemically addressable trisradical rotaxanes. Trivalent metal cations, yttriumiii and smaller lanthanides, are used to. Eliminating the need for independent counterions in the construction of metal organic rotaxane frameworks morfs lisa k. Metal organic frameworks pablo martinezbulit,1 alexander j. Synthesis, characterization and application of metal organic frameworks by lingjuan shen dissertation submitted in the partial fulfillment of the requirements for the degree of doctor of philosophy in chemistry in the graduate college of the university of illinois at urbanachampaign, 2012 urbana, illinois doctoral committee. Electrochemically addressable trisradical rotaxanes. Four novel highdimensional metal organic rotaxane frameworks morfs were successfully fabricated by cucurbit6urilbased pseudorotaxanes pr43 and rigid carboxylate ligands by adjusting the synthesis temperature and the length of ligands. The structure has a unique lattice, in which three independent 3. Metal organic frameworks mofs are a class of microporous crystalline materials consisting of a highly ordered extended network of metal ions or clusters coordinated to multidentate organic molecules 100. Metal organic frameworks mofs are porous crystalline materials of one, two, or threedimensional.
Rotaxane monoand multilayers are shown to reversibly switch in a coupled manner between two ordered states as revealed by linear dichroism. Synthesis and characterization of metalorganic frameworks. Jonathan melville a thesis submitted in partial ful llment of the requirements for the degree of bachelor of science with honors in chemistry, under the supervision of professor je rey r. Syntheses and magnetic properties of highdimensional. While both the oxidation and demetalation experiments have been demonstrated to occur without disrupting the crystallinity of the frameworks, the fact that at least. Synthesis, structure, and dynamic properties of hybrid organic inorganic rotaxanes. Metal organic rotaxane frameworks assembly by cucurbit6. Metal organic framework an overview sciencedirect topics. The present system represents supramolecular chemistry. Synthesis and characterization of metalorganic frameworks for gas storage and separations author. A linear multiporphyrinic 2 rotaxane via amide bond. Metalorganic frameworks with mechanically interlocked.
A pomencapsulating 3d porous metal organic pseudo rotaxane framework haijun pang,a jun peng,a chunjing zhang,a yangguang li,a pengpeng zhang,a huiyuan ma,b and zhongmin sua table of the contents. When cadmiumii is used as the metal center the resulting structure is a network in which two 2pseudorotaxanes, two naked axles and two. In the last decade these microporous materials have found several. A tetracarboxylate 2 rotaxane linker with a 24crown6 ether 24c6 macrocycle was prepared. Synthesis, structure, and dynamic properties of hybrid. Metal organic frameworks mofs ae mr ade by linking inogranic and organic units by str ong bonds r eticular syn thesis. This compound was prepared by a slight modification of the literature method y. Metal organic frameworks mofs are made by linking inorganic and organic units by strong bonds reticular synthesis.
Aniondirected assembly of a threedimensional metal. The singlecrystal xray structures of mofs uwdm2 1,4. A metal organic framework with a 2 rotaxane as a building block demonstrates that such dynamic processes can also operate inside a solidstate material. Robust zr iv carboxylate bonds are forged between the zr clusters of nu and carboxylic acid groups of rotaxane precursors semirotaxanes as part of this building block. A threedimensional extended, metalorganic rotaxane framework morf that incorporates encircled struts has been synthesized through a onepot selfassembly process involving a macrocyclic tetraimidazolium molecular box, naphthalene dicaboxylate dianion, and znii cations. The chemistry and applications of metalorganic frameworks. Metal ion directed metalorganic rotaxane frameworks with.
The work herein, describes the placement of mechanically interlocked molecules mims into ordered, crystalline metal organic frameworks mofs to create metal organic rotaxane frameworks morfs. The focus of this thesis is the incorporation of the 1,2bispyridiniumethane motif into new 2 rotaxane ligands for the purpose of developing new metal organic rotaxane frameworks morfs. The flexibility with which the constituents geometry, size, and functionality can be varied has led to more than 20,000 different mofs being reported and studied within the past decade. Syntheses and magnetic properties of highdimensional cucurbit6urilbased metal organic rotaxane frameworks xuesong wu, a hongfei bao, b fulong zhu, b jing sun, a xinlong wang ab and zhongmin su ab. Protection of metals and physical chemistry of surfaces 2017, 53 5, 937949.
These systems consist of biscarboxylate anions threaded through the core of tetraimidazolium macrocycles. The organization of trisradical rotaxanes within the channels of a zr6based metal organic framework nu has been achieved postsynthetically by solventassisted ligand incorporation. Three novel selfcatenated 4connected uninodal 658mok metal organic rotaxane frameworks morfs containing cucurbit6uril were constructed from the in situ transcisconfiguration 1. Rotaxane ligands for incorporation into metalorganic. The new mofs, uwdm8 and uwdm9, cooperative phenomena in framework materials. The organization of trisradical rotaxanes within the channels of a zr 6based metal organic framework nu has been achieved postsynthetically by solventassisted ligand incorporation.
Nicholas vukotic, elizabeth viljoen, christopher b. The structural characterization of mof1040, based on xray structural analysis, shows that these struts form threefold interpenetrated pcu networks. Compound 1 represents a three periodic 2fold interpenetrating dia network based on a binuclear cd2cl4o4 second building unit sbu. The 2pseudorotaxane formed between the dicationic axle 1,2bis4,4. Loeb, linking 2 rotaxane wheels to create a new type of metal organic rotaxane framework chem. The mim linker is a 2 rotaxane with a 24crown6 24c6 macrocycle and an anilinebased axle with terminal pyridine donor groups. Rotaxanes as ligands for molecular machines and metal.
Metal organic frameworks with dynamic interlocked components v. Weak functional group interactions revealed through metal. Hybrid organicinorganic rotaxanes and molecular shuttles. Formation of a polythreaded, metal organic framework. Lynch,a xiaoyang zhu,a moonhyun oh,b, and jonathan l. Metalorganic frameworks incorporating coppercomplexed. View enhanced pdf access article on wiley online library html view.
The mim linker is a 2 rotaxane with a 24crown6 24c6 macrocycle and. Unprecedented 4 and 6connected 2d coordination networks. Pdf metalorganic frameworks synthesis and applications. Zriv metal organic frameworks mofs uio68 and pcn57, containing linkers triphenylene dicarboxylate tpdc and tetramethyltriphenylene dicarboxylate ttdc, respectively, were doped with an h shaped, tetracarboxylate linker that contains a 2 rotaxane molecular shuttle. Eliminating the need for independent counterions in the. A linear multiporphyrinic 2 rotaxane has been synthesized using the transition metal templating method for threading a goldiiiincorporating macrocycle onto a rodlike, phenanthrolinederived chelate bearing carboxylate end groups. For metal organic rotaxane frameworks morfs, one, two, and threedimensional arrays of organic rotaxanes linked by metal coordination bonds, see. Mechanically interlocked molecules such as rotaxanes and catenanes have been studied in solution as possible simple molecular switches and machines, but in this medium, the molecules are randomly dispersed and their motion incoherent chemists at the university of windsor, ontario, canada, have synthesized metal organic framework mof materials using a 2 rotaxane as the organic linker. A hexacarboxylate ligand based on an interlocked 2 rotaxane motif is used to construct a zn ii metal organic framework material. Metal organic frameworkssynthesis and applications 83 3. A new metal organic framework based on cadmium thiocyanate and 6methylequinoline as corrosion inhibitor for copper in 1 m hcl solution.
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