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(12) Patent Application Publication (10) Pub. No.: US 2013/0184456A1 ZAWOROTKO Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2013/0184456A1 ZAWOROTKO Et Al US 2013 O184456A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2013/0184456A1 ZAWOROTKO et al. (43) Pub. Date: Jul.18, 2013 (54) HETEROCYCLIC MACROCYCLE C07F 13/00 (2006.01) TEMPLATED METAL-ORGANIC C07F 15/04 (2006.01) MATERLALS C07F 3/08 (2006.01) (75) Inventors: Michael John ZAWOROTKO, Tampa, C07F 15/02 (2006.01) FL (US); Zhenjie Zhang, Tampa, FL (52) U.S. Cl. (US); Randy W. Larsen, Tampa, FL CPC ................. C07F 15/065 (2013.01); C07F 3/08 (US); Mohamed Eddaoudi, Tampa, FL (2013.01); C07F 3/06 (2013.01); C07F 15/025 (US); Linping Zhang, Tampa, FL (US); (2013.01); C07F 13/005 (2013.01); C07F Lukasz Wojtas, Tampa, FL (US) 15/045 (2013.01); C07F 3/02 (2013.01) (73) Assignee: UNIVERSITY OF SOUTH USPC .......................................................... 540/145 FLORIDA, Tampa, FL (US) (21) Appl. No.: 13/528,136 (57) ABSTRACT (22) Filed: Jun. 20, 2012 Related U.S. Application Data A process for the preparation of a heterocyclic macrocycle (60) Provisional application No. 61/499,140, filed on Jun templated Supramolecular metal organic material, the process 20, 2011 pp s u. I ws comprising preparing a reaction mixture containing a metal, a s heterocyclic macrocycle, and organic ligands and forming, in Publication Classification the reaction mixture, a heterocyclic macrocycle-templated metal organic material comprising the metal, the heterocyclic (51) Int. Cl. macrocycle and the ligands by template-directed synthesis C07F 15/06 (2006.01) with the heterocyclic macrocycle serving as the template and C7F 3/06 (2006.01) being encapsulated within a cage of the template metal C07F 3/02 (2006.01) organic material. Patent Application Publication Jul.18, 2013 Sheet 1 of 19 US 2013/O18445.6 A1 MBB it of hits Number of structures for specific metals Square paddlewheel 2075 Cu(1027), Rh(414), Ru(212), Mo(125), (M(COO)4 Zn(68), Fe(52), Cr(48), Co(26), Ni(25), W(21), Mn(10), Re(10), Ca(7), W(6), Bi(6), Tc(6), Os(5), Ti(4), Pt(3), Hg(2), n(1), x: Mg(1), Al(1), Sc(1) Octahedral 5813 Ru(1375), Co(768), Ni(754), Fe(674), M(py)4(nM)2 Cu(589), Mn(490), Zn(398), Cod(254), nM. non-metaic Os(91), ir(77), Cr(71), Rh(56), V(47), elements Re(28), Pb(24), Hg (22), Ga(18), Mo(17), Tc(17), Yb(8), Ti(7), A1(7), Na(6), Ag(5), Mg(4), W(4), Nb(3), Pt(3), Eu(2), in (2), Pa(1), Sn(1), T(1), Ca(1), K(1), Zr(1), Sm(1) Trigonal prism 497 Fe(170), Cr(80), Mn(47), Ru(41), Mo(22), M3O(COO)s. W(23), W(17), ir(4), Nb(4), Co(3), Rh(3), . Be(3), Ni(2), n(2), A(2), Sc(1), Zn(1) Octahedron 50 Zn(42), Co(3), Be (3), Cu(2) (M.O(COO)) FIG. Patent Application Publication Jul.18, 2013 Sheet 2 of 19 US 2013/O18445.6 A1 d 2SS13S ( s' s N g s R. SS SS A. aS a s & O EYQ,QN S.As -- s a- NNS 2SSe SN at t y g? VVSA S1) SS YS FIG. 2 Patent Application Publication Jul.18, 2013 Sheet 3 of 19 US 2013/O18445.6 A1 FIG. 3 Patent Application Publication Jul.18, 2013 Sheet 4 of 19 US 2013/O18445.6 A1 FIG. 4 Patent Application Publication Jul.18, 2013 Sheet 5 of 19 US 2013/O18445.6 A1 s E.S S(NA^ FIG. 5 Patent Application Publication Jul.18, 2013 Sheet 6 of 19 US 2013/O18445.6 A1 FIG. 6 Patent Application Publication Jul.18, 2013 Sheet 7 of 19 US 2013/O18445.6 A1 FIG. 7 Patent Application Publication Jul.18, 2013 Sheet 8 of 19 US 2013/O18445.6 A1 FIG. 8 Patent Application Publication Jul.18, 2013 Sheet 9 of 19 US 2013/O18445.6 A1 FIG. 9 Patent Application Publication Jul.18, 2013 Sheet 10 of 19 US 2013/O18445.6 A1 FIG. 10 Patent Application Publication Jul.18, 2013 Sheet 11 of 19 US 2013/O18445.6 A1 FIG 11 Patent Application Publication Jul.18, 2013 Sheet 12 of 19 US 2013/O18445.6 A1 FIG. 12 Patent Application Publication Jul.18, 2013 Sheet 13 of 19 US 2013/O18445.6 A1 Patent Application Publication Jul.18, 2013 Sheet 14 of 19 US 2013/O18445.6 A1 FIG. 14 Patent Application Publication Jul.18, 2013 Sheet 15 of 19 US 2013/O18445.6 A1 FIG. 15 Patent Application Publication Jul.18, 2013 Sheet 16 of 19 US 2013/O18445.6 A1 FIG 16 Patent Application Publication Jul.18, 2013 Sheet 17 of 19 US 2013/O18445.6 A1 FIG. 17 Patent Application Publication Jul.18, 2013 Sheet 18 of 19 US 2013/O18445.6 A1 Patent Application Publication Jul.18, 2013 Sheet 19 of 19 US 2013/O18445.6 A1 FIG. 19 US 2013/018445.6 A1 Jul. 18, 2013 HETEROCYCLIC MACROCYCLE reactions occur only at their surfaces; porph(a)MOMs were TEMPLATED METAL-ORGANIC previously limited to a small set of existing MOMs that have MATERALS the right type of cavity to selectively encapsulate a porphyrin molecule. CROSS REFERENCE TO RELATED 0007. Design principles that are based upon the concepts APPLICATIONS of crystal engineering and self-assembly have recently 0001. This application claims priority to U.S. Provisional afforded new classes of crystalline Solids that possess impor Application Ser. No. 61/499,140, filed Jun. 20, 2011 and tant physical properties such as bulk magnetism or porosity. additionally claims priority to U.S. application Ser. No. Large-scale molecular networks have been developed to 13/412,308, filed Mar. 5, 2012, which claims priority to U.S. encapsulate other materials and these are playing an ever Provisional Application No. 61/448,974, filed Mar. 3, 2011, increasing role in the pharmaceutical industry and as materi each of which is incorporated herein by reference in its als for sensors, and liquid crystals. In addition, with the inclu entirety. sion of metals within the structures, the large polymers formed by these crystals can possess, among other properties, FIELD OF THE INVENTION catalytic, fluorescent, and magnetic attributes. 0002 The present invention generally relates to supramo SUMMARY OF THE INVENTION lecular assemblies, and their modes of synthesis. 0008 Among the various aspects of the present invention BACKGROUND OF THE INVENTION is the provision of a template-directed synthetic process for the preparation of metal organic materials; the provision of 0003 Porphyrins are remarkable and versatile ligands for Such a process for the formation of a product in which any of transition metals and metalloporphyrins have found a wide a class of heterocyclic macrocycles is encapsulated because range of applications in enzymatic reactions and biomimetic/ of shape and/or noncovalent bonds between the heterocyclic industrial chemistry." Metal-Organic Materials (MOMs) are macrocycle and the framework of the metal-organic material. comprised of metals or metal clusters (“nodes') coordinated 0009 Briefly, therefore, the present invention is directed to multi-functional organic ligands (“linkers”); and they to a process for the preparation of a heterocyclic macrocycle offer unparalleled levels of permanent porosity (there are templated Supramolecular metal organic material. The pro numerous MOMs with BET Surface areas in the 3000-6000 cess comprises preparing a reaction mixture containing a migrange). Furthermore, the modular nature of MOMs and metal, a heterocyclic macrocycle, and organic ligands and their use of known coordination chemistry offer enormous forming, in the reaction mixture, a heterocyclic macrocycle diversity of structures and properties." templated metal organic material comprising the metal, the 0004. In principle, metal-organic materials (MOMs) that heterocyclic macrocycle and the ligands by template-directed are based upon polyhedral cages' offerexcellent platforms synthesis with the heterocyclic macrocycle serving as the for the development of porph?a MOM heterogeneous cata template. lytic systems since certain polyhedral MOMs contain cages 0010. Another aspect of the present invention is a process with the requisite symmetry and size to accommodate a cata for the preparation of a heterocyclic macrocycle-templated lytic metalloporphyrin in a “ship-in-a-bottle' fashion and Supramolecular metal organic material. The process com pores that facilitate ingress of Substrate and egress of product. prises (i) preparing a reaction mixture containing a metalated 0005 Porphyrin encapsulation (as opposed to porphyrin heterocyclic macrocycle, organic ligands and a metal, the walled MOMs prepared from custom-designed porphyrins') metalated heterocyclic macrocycle coordinating a first metal, and catalytic activity has thus far been demonstrated in only (ii) forming a metalated heterocyclic macrocycle-templated three MOMs: a discrete pillared coordination box, the pro Supramolecular metal organic material comprising the metal, totypal' polyhedral MOMHKUST-1" and a zeolitic metal the metalated heterocyclic macrocycle and the ligands in the organic framework that exhibits rho-Zeolite topology.'" reaction mixture by template-directed synthesis with the HKUST-1 is formed via assembly of benzene-1,3,5-tricar metalated heterocyclic macrocycle serving as the template, boxylate (BTC) anions and Cu" (HKUST-1-Cu)'', Zn and (iii) exchanging the first metal coordinated by the meta (HKUST-1-Zn)', Fe?"/Fe (HKUST-1-Fe)' or Nit lated heterocyclic macrocycle of the metalated heterocyclic (HKUST-1-Ni)7 cations, and is well-suited to serve as a macrocycle-templated Supramolecular metal organic mate platform for catalysis since its topology affords three distinct rial with a second metal, the first and second metals being polyhedral cages capable of entrapping guest molecules. different. Indeed, HKUST-1-Cu selectively encapsulates polyoxomet 0011. Another aspect of the invention is the preparation of allate anions and exhibits size selective catalysis of ester metal-organic materials in which a heterocyclic macrocycle hydrolysis." However, the number of metals that can form is encapsulated rather than part of the metal-organic material.
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