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 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 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. structures with HKUST-1 topology is rather limited because Advantageously, such materials may be used in a wide range HKUST-1 is built from a “square paddlewheel node that is of applications including, for example, catalysis, separations, not readily accessible for metals other than Cu" and Zn". Meso-tetra(N-methyl-4-pyridyl) tetratosylate and sensing. (TMPyP) has been widely studied as a catalyst' and it can be 0012. Other objects and features will be in part apparent encapsulated within the medium-sized octahemioctahedral and in part pointed out hereinafter. cage of HKUST-1-Cu.' 0006 Existing porphyrin catalysts can suffer from the fol ABBREVIATIONS AND DEFINITIONS lowing problems: homogeneous porphyrin catalysts tend not 0013 The following definitions and methods are provided to have long lifetimes because they are reactive; heteroge to better define the present invention and to guide those of neous catalysts typically exhibit low rates of reaction because ordinary skill in the artin the practice of the present invention. US 2013/018445.6 A1 Jul. 18, 2013

Unless otherwise noted, terms are to be understood according from two to eight carbon atoms in the principal chain and up to conventional usage by those of ordinary skill in the relevant to 20 carbon atoms. They may be straight or branched chain art. and include ethynyl, propynyl, butynyl, isobutynyl, hexynyl, 0014. The following definitions and methods are provided and the like. to better define the present invention and to guide those of 0023 The terms “amine” or “amino,” as used herein alone ordinary skill in the art in the practice of the present invention. or as part of another group, represents a group of formula Unless otherwise noted, terms are to be understood according —NCXs)(X), wherein Xs and X are independently hydro to conventional usage by those of ordinary skill in the relevant gen, hydrocarbyl, substituted hydrocarbyl, heteroaryl, or het art. erocyclo, or Xs and Xo taken together form a Substituted or 0.015 The terms “acetal' and “ketal,” as used herein alone unsubstituted alicyclic, aryl, or heterocyclic moiety, each as or as part of another group, denote the moieties represented defined in connection with Such term, typically having from 3 by the following formulae, respectively: to 8 atoms in the ring. “Substituted amine.” for example, refers to a group of formula —NCXs)(X), wherein at least one of Xs and X are other than hydrogen. “Unubstituted K. K. amine.” for example, refers to a group of formula —NCXs) -OX -OX (X), wherein Xs and X are both hydrogen. H X 0024. The terms "amido’ or "amide,” as used herein alone or as part of another group, represents a group of formula acetal ketal —CONCXs)(X), wherein X and X are as defined in con nection with the terms "amine' or "amino.” “Substituted wherein X and X are independently hydrocarbyl, substi amide.” for example, refers to a group of formula—CONCXs) tuted hydrocarbyl, heterocyclo, or heteroaryl, and X is (X), wherein at least one of Xs and X are other than hydro hydrocarbyl or substituted hydrocarbyl, as defined in connec gen. “Unsubstituted amido.” for example, refers to a group of tion with Such terms, and the wavy lines represent the attach formula—CONCX)(X), wherein X and X are both hydro ment point of the acetal or ketal moiety to another moiety or gen compound. (0025. The terms “aryl” or “Aras used herein alone or as 0016. The term “acyl as used herein alone or as part of part of another group denote optionally substituted homocy another group, denotes the moiety formed by removal of the clic aromatic groups, preferably monocyclic or bicyclic hydroxy group from the group —COON of an organic car groups containing from 6 to 12 carbons in the ring portion, boxylic acid, e.g., XC(O)—, wherein X is X', X'O , Such as phenyl, biphenyl, naphthyl, Substituted phenyl, Sub X'XN-, or X'S , X is hydrocarbyl, heterosubstituted stituted biphenyl or substituted naphthyl. Phenyl and substi hydrocarbyl, or heterocyclo, and R is hydrogen, hydrocarbyl tuted phenyl are the more preferred aryl. or substituted hydrocarbyl. Exemplary acyl moieties include acetyl, propionyl, benzoyl pyridinylcarbonyl, and the like. 0026. The term “arylene', as used herein alone or part of 0017. The term “acyloxy.” as used herein alone or as part another group refers to a divalentaryl radical of one to twelve of another group, denotes an acyl group as described above carbon atoms. Non-limiting examples of “arylene' include bonded through an oxygen linkage (—O—), e.g., XC(O) phenylene, pyridinylene, pyrimidinylene and thiophenylene. O— wherein X is as defined in connection with the term (0027. The terms “alkaryl” or “alkylaryl,” as used herein “acyl alone or as part of another group, denotes an -(arylene)-X 0018. The term “alkoxy, as used herein alone or as part of radical, wherein X is as defined in connection with the term another group, denotes an —OX radical, wherein X is hydrocarbyl or substituted hydrocarbyl. 0019. Unless otherwise indicated, the alkyl groups 0028. The term "” refers to a compound compris described herein are preferably lower alkyl containing from ing a fundamental skeleton of three nuclei and one one to eight carbon atoms in the principal chain and up to 20 pyrroline united through the C-positions by methane groups carbon atoms. They may be straight or branched chain or to form the following macrocyclic structure: cyclic and include methyl, ethyl, propyl, isopropyl, butyl, hexyl and the like. 0020. The term “alkylene, as used herein alone or as part of another group, denotes a linear Saturated divalent hydro carbon radical of one to eight carbon atoms or a branched saturated divalent hydrocarbon radical of three to six carbon atoms unless otherwise stated. Exemplary alkylene moieties 20 10. include methylene, ethylene, propylene, 1-methylpropylene, 2-methylpropylene, butylene, pentylene, and the like. 0021. Unless otherwise indicated, the alkenyl groups described herein are preferably lower alkenyl containing 15 from two to eight carbon atoms in the principal chain and up to 20 carbonatoms. They may be straight or branched chain or cyclic and include ethenyl, propenyl, isopropenyl, butenyl, 0029. The term “” refers to a compound comprising isobutenyl, hexenyl, and the like. a fundamental skeleton of three pyrrole nuclei and one pyr 0022. Unless otherwise indicated, the alkynyl groups roline united through the C-positions by methane groups to described herein are preferably lower alkynyl containing form the following macrocyclic structure: US 2013/018445.6 A1 Jul. 18, 2013

0039. The terms “heterocyclo” or "heterocyclic” as used herein alone or as part of another group denote optionally Substituted, fully saturated or unsaturated, monocyclic or bicyclic, aromatic or nonaromatic groups having at least one heteroatom in at least one ring, and preferably 5 or 6 atoms in each ring. The heterocyclogroup preferably has 1 or 2 oxygen atoms, 1 or 2 sulfur atoms, and/or 1 to 4 nitrogenatoms in the ring, and may be bonded to the remainder of the molecule through a carbon or heteroatom. Exemplary heterocyclo include heteroaromatics Such as furyl, thienyl, pyridyl, oxazolyl, pyrrolyl, indolyl, quinolinyl, or isoquinolinyl and 0030 The term “cyano.” as used herein alone or as part of the like. Exemplary substituents include one or more of the another group, denotes a group of formula—CN. following groups: hydrocarbyl, Substituted hydrocarbyl, 0031. The term “carbocyclic” as used herein alone or as keto, hydroxy, protected hydroxy, acyl, acyloxy, alkoxy, alk part of another group refers to a saturated or unsaturated enoxy, alkynoxy, aryloxy, halogen, amido, amino, nitro, monocyclic or bicyclic ring in which all atoms of all rings are cyano, thiol, ketals, acetals, esters and ethers. carbon. Thus, the term includes cycloalkyl and aryl rings. The 0040. The terms “hydrocarbon” and “hydrocarbyl” as carbocyclic ring(s) may be substituted or unsubstituted. used herein describe organic compounds or radicals consist Exemplary substituents include one or more of the following ing exclusively of the elements carbon and hydrogen. These groups: hydrocarbyl, Substituted hydrocarbyl, keto, hydroxy, moieties include alkyl, alkenyl, alkynyl, and aryl moieties. protected hydroxy, acyl, acyloxy, alkoxy, alkenoxy, alkynoxy, These moieties also include alkyl, alkenyl, alkynyl, and aryl aryloxy, halogen, amido, amino, nitro, cyano, thiol, ketals, moieties substituted with other aliphatic or cyclic hydrocar acetals, esters and ethers. bon groups, such as alkaryl, alkenaryland alkynaryl. Unless 0032. The term “cycloalkyl, as used herein alone or as part of another group, denotes a cyclic Saturated monovalent otherwise indicated, these moieties preferably comprise 1 to bridged or non-bridged hydrocarbon radical of three to ten 20 carbon atoms. carbon atoms. Exemplary cycloalkyl moieties include cyclo 0041. The term “hydroxy.” as used herein alone or as part propyl, cyclobutyl, cyclopentyl, cyclohexyl, or adamanty1. of another group, denotes a group of formula —OH. Additionally, one or two ring carbonatoms may optionally be 0042. The term “keto.” as used herein alone or as part of replaced with a CO— group. another group, denotes a double bonded oxygen moiety (i.e., 0033. The term “ester as used herein alone or as part of =O). another group, denotes a group of formula —COOX 0043. The term “meso refers to the position on the por wherein X is alkyl or aryl, each as defined in connection phyrin, porphyrazin, chlorin, corrin and struc with such term. ture adjacent to the reduced pyrrole ring, i.e., positions 5, 10. 0034. The term “ether,” as used herein alone or as part of 15, and 20 of the porphyrin macrocycle (and the correspond another group, includes compounds or moieties which con ing carbon or nitrogen atoms in the porphyrazin, chlorin, tain an oxygen atom bonded to two carbon atoms. For corrin and porphyrinogen macrocyclic structures). Stated dif example, ether includes “alkoxyalkyl which refers to an ferently, a “meso-porphyrin' is a porphyrin compound com alkyl, alkenyl, or alkynyl group Substituted with an alkoxy prising Substituent groups at the 5, 10, 15, and 20 position, or group. combinations thereof, a “meso-porphyrazin' is a porphyrazin 0035. The terms “halide,” “halogen” or “halo' as used compound comprising Substituent groups at the nitrogen herein alone or as part of another group refer to chlorine, atoms adjacent the pyrrole rings, a “meso-chlorin' is a chlorin bromine, fluorine, and iodine. compound comprising Substituent groups at the carbonatoms 0036. The term "heteroatom' shall mean atoms other than adjacent the pyrrole rings, a “meso-corrin' is a corrin com carbon and hydrogen. pound comprising Substituent groups at the carbon atoms 0037. The term “heteroaromatic' or “heteroaryl” as used adjacent the pyrrole rings, and “meso-pyrophyrinogen' is a herein alone or as part of another group denote optionally pyrophyrinogen compound comprising Substituent groups at Substituted aromatic groups having at least one heteroatom in the carbon atoms adjacent the pyrrole rings. at least one ring, and preferably 5 or 6 atoms in each ring. The 0044) The term “metalated heterocyclic macrocycle” as heteroaromatic group preferably has 1 or 2 oxygen atoms, 1 used herein denotes a heterocyclic macrocycle containing a or 2 sulfur atoms, and/or 1 to 4 nitrogenatoms in the ring, and coordinated metal, the metal being coordinated, for example, may be bonded to the remainder of the molecule through a by two or more of the nitrogen atoms at the 21, 22, 23, or 24 carbon or heteroatom. Exemplary heteroaromatics include position of a porphyrin (a metalated porphyrin) or the corre furyl, thienyl, pyridyl, oxazolyl pyrrolyl, indolyl, quinolinyl, sponding nitrogen atoms of a porphyrazin (a metalated por or isoquinolinyl and the like. Exemplary Substituents include phyrazin), a chlorin (a metalated chlorin), a corrin (a meta one or more of the following groups: hydrocarbyl, Substituted lated corrin) and a porphyrinogen (a metalated hydrocarbyl, keto (i.e., =O), hydroxy, protected hydroxy, porphyrinogen). acyl, acyloxy, alkoxy, alkenoxy, alkynoxy, aryloxy, halogen, 0045. The term “metalloporphyrin as used herein is used amido, amino, nitro, cyano, thiol, ketals, acetals, esters and interchangeably with metalated porphyrin. ethers. 0046. The term "nitro, as used herein alone or as part of 0038. The term "heteroarylene' as used herein alone or as another group, denotes a group of formula —NO. part of another group refers to a divalent heteroaryl radical. 0047. The term “porphyrazin’ refers to a compound com Non-limiting examples of "heteroarylene' include furylene, prising a fundamental skeleton of four pyrrole nuclei united thienylene, pyridylene, oxazolylene, pyrrolylene, indolylene, through the C-positions by four amine groups to form the quinolinylene, or isoquinolinylene and the like. following macrocyclic structure: US 2013/018445.6 A1 Jul. 18, 2013

alkylthioalkynyls. The term “alkylthioalkyls' includes com pounds with an alkyl, alkenyl, or alkynyl group bonded to a sulfur atom that is bonded to an alkyl group. Similarly, the term “alkylthioalkenyls' and alkylthioalkynyls' refer to com pounds or moieties where an alkyl, alkenyl, or alkynyl group is bonded to a sulfur atom that is covalently bonded to an alkynyl group. 0.052 The term “thiol, as used herein alone or as part of another group, denotes a group of formula—SH. BRIEF DESCRIPTION OF THE DRAWINGS 0053 FIG. 1 is Cambridge Structural Database analysis of 0048. The term “porphyrin refers to a compound com the occurrence (it of hits) of four examples of molecular prising a fundamental skeleton of four pyrrole nuclei united building blocks that can serve as nodes for construction of through the C-positions by four methane groups to form the porpha MOMs. following macrocyclic structure: 0054 FIG. 2 is a three dimensional framework of Por(a)MOM-1 as described more fully in Example 1. 0055 FIG. 3 is a three dimensional framework of Por(a)MOM-2 as described more fully in Example 2. 5 0056 FIG. 4 is a three dimensional framework of Por(a)MOM-3 as described more fully in Example 3. 0057 FIG. 5 is a three dimensional framework of Por(a)MOM-4 as described more fully in Example 4. 0058 FIG. 6 is a three dimensional framework of Por(a)MOM-5 as described more fully in Example 5. 0059 FIG. 7 is a three dimensional framework of Por(a)MOM-6 as described more fully in Example 6. C15 0060 FIG. 8 is a three dimensional framework of Por(a)MOM-7 as described more fully in Example 7. 0049. The term “porphyrinogen' refers to a compound 0061 FIG. 9 is a three dimensional framework of comprising a fundamental skeleton of four pyrrole nuclei Por(a)MOM-8 as described more fully in Example 8. united through the C-positions by four methane groups to 0062 FIG. 10 is a three dimensional framework of form the following macrocyclic structure: Por(a)MOM-9 as described more fully in Example 9. 0063 FIG. 11 is a three dimensional framework of Por(a)MOM-11 as described more fully in Example 11. 0064 FIG. 12 is a three dimensional framework of Por(a)MOM-12 as described more fully in Example 12. 0065 FIG. 13 is a three dimensional framework of Por(a)MOM-13 as described more fully in Example 13. 0.066 FIG. 14 is a three dimensional framework of 20 10. Por(a)MOM-14 as described more fully in Example 14. y(4)K "Sr.x 5 Y4 .. 0067 FIG. 15 is a three dimensional framework of Por(a)MOM-15 as described more fully in Example 15. 0068 FIG. 16 is a three dimensional framework of 15 Por(a)MOM-16 as described more fully in Example 16. 0069 FIG. 17 is a three dimensional framework of 0050. The “substituted hydrocarbyl moieties described Por(a)MOM-17 as described more fully in Example 17. herein are hydrocarbyl moieties which are substituted with at 0070 FIG. 18 is a three dimensional framework of least one atom other than carbon, including moieties in which Por(a)MOM-18 as described more fully in Example 18. a carbon chain atom is substituted with a hetero atom Such as (0071 FIG. 19 is a three dimensional framework of nitrogen, oxygen, silicon, phosphorous, boron, Sulfur, or a Por(a)MOM-19 as described more fully in Example 19. halogen atom. These Substituents include halogen, heterocy clo, alkoxy, alkenoxy, alkynoxy, aryloxy, hydroxy, protected DETAILED DESCRIPTION OF THE INVENTION hydroxy, keto, acyl, acyloxy, nitro, amino, amido, nitro, 0072. In accordance with one aspect of the present inven cyano, thiol, ketals, acetals, esters, ethers, and thioethers. tion, a porphyrin serves as a template in a template-directed 0051. The term “thioether,” as used herein alone or as part synthesis of a metal organic material with a heterocyclic of another group, denotes compounds and moieties that con macrocycle template being encapsulated in cages present in tain a sulfur atom bonded to two different carbon or hetero the final product. Without being bound to any particular atoms (i.e., —S-), and also includes compounds and moi theory, and based upon evidence to-date, the heterocyclic eties containing two Sulfur atoms bonded to each other, each macrocycle template appears to “hold the reactive sites of of which is also bonded to a carbon or hetero atom (i.e., the reactants close together, facilitating the creation of a cage dithioethers ( S S )). Examples of thioethers include, that is customized for the particular heterocyclic macrocycle but are not limited to, alkylthioalkyls, alkylthioalkenyls, and template. Advantageously, this synthetic approach may be US 2013/018445.6 A1 Jul. 18, 2013

used to prepare metal organic materials that cannot be made cycle is formed, the metal coordinated by the metalated het by other synthetic methods because, for example, the desired erocyclic macrocycle is exchanged with another (different) cage structure is thermodynamically or kinetically disfa metal. By way of further example, in one embodiment the first Vored; it may also serve to minimize side reactions, lowering metal, i.e., the metal coordinated by the metalated heterocy the activation energy of the reaction, and producing desired clic macrocycle comprised by the reaction mixture is cad stereochemistry. The template effect is well-known in Zeolite mium, and the second metal, i.e., the metal coordinated by the chemistry wherein the template is sometimes called a struc metalated heteocyclic macrocycle of the Supramolecular ture directing agent. metal organic material formed in the reaction is 0073 Independent of any theory, in a typical process a or a transition metal. heterocyclic macrocycle, a metal, and an organic ligand are 0075 Another aspect of the present invention is a process combined in a solvent system to form a reaction mixture and for the preparation of a heterocyclic macrocycle-templated the reaction mixture is preferably heated to form the hetero Supramolecular metal organic material. The process com cyclic macrocycle-templated Supramolecular metal organic prises (i) preparing a reaction mixture containing a metalated material. As described in greater detail herein, the metal is heterocyclic macrocycle, organic ligands and a metal, (ii) preferably introduced to the mixture inform of a metal salt, a forming, in the reaction mixture, a metalated heterocyclic metal oxide, or a combination thereof, and the heterocyclic macrocycle-templated metal organic material comprising the macrocycle is introduced to the mixture as a metalated het metal, the metalated heterocyclic macrocycle and the ligands erocyclic macrocycle, a non-metalated heterocyclic macro by template-directed synthesis with the metalated heterocy cycle (i.e., a heterocyclic macrocycle not having a metal clic macrocycle serving as the template, and (iii) exchanging coordinated by two or more of the atoms of the heterocyclic the metal coordinated by the metalated heterocyclic macro macrocycle, e.g., by the nitrogenatoms at the 21, 22, 23, or 24 cycle with a second metal. position of a porphyrin or the corresponding carbon or nitro 0076. In general, the molecular building blocks are com gen atoms of a porphyrazin, chlorin, corrin or porphyrino prised of metals or metal clusters with three or more connec gen), or a combination thereof. The resulting metal organic tion points (nodes) and they are coordinated to multi-func material comprises molecular building blocks, derived from tional exodentate organic ligands. If the organic ligands are the metal and organic ligands in the reaction mixture, and bifunctional and their only role is to connect two adjacent cavities enclosed by the molecular building blocks, in which nodes then they serve as “linkers' whereas polyfunctional a metalated heterocyclic macrocycle resides. In one embodi ligands that connect three or more nodes also serve as nodes. ment, the metal ions comprised by the molecular building In general, the cavities in the Supramolecular assemblies will blocks and the metal ions comprised by the metalated hetero have the requisite shape, size and symmetry to encapsulate a cyclic macrocycle are the same. In another embodiment, the particular metalated heterocyclic macrocycle and will have metal ions comprised by the molecular building blocks and windows that allow ingress reaction Substrates and egress of the metal ions comprised by the metalated heterocyclic mac reaction products. rocycle in the supramolecular assembly are different. In yet 0077 Reaction temperatures will typically be in the range another embodiment, the molecular building blocks and the of about 0 to 200° C. More typically, the reaction temperature metalated heterocyclic macrocycle in the Supramolecular will be in the range of about 20 to 120° C. Alternatively, or assembly independently comprise two or more different additionally, in Some embodiments the reaction mixture may metal ions. be microwaved to induce the formation of the supramolecular 0074. In one embodiment, the heterocyclic macrocycle assembly. templated Supramolecular metal organic material heterocy 0078. The reaction mixture solvent system will typically clic macrocycle is derived from a reaction mixture compris comprise a Suitable organic solvent. It may additionally com ing a metalated heterocyclic macrocycle, a metal (preferably prise water. Exemplary organic solvents include, but are not in the form of a metal salt, metal oxide or combination limited to, aprotic dipolar solvents (such as acetone, acetoni thereof), and organic ligand and, after the Supramolecular trile, dimethylformamide, dimethylacetamide, dimethylsul metal organic material heterocyclic macrocycle is formed, foxide, 1-methyl-2-pyrrolidinone, and the like), alcohols the metal coordinated by the metalated heterocyclic macro (such as methanol, ethanol, tert-butanol, isopropanol, and the cycle is exchanged with another (different) metal. For like), combinations thereof, and the like. Preferred reaction example, the metalated heterocyclic macrocycle introduced mixture solvent systems comprise dimethylacetamide to the reaction mixture may comprise a first metal selected, ("DMA"), dimethylformamide (“DMF'), and/or "DEF" with for example, from Groups 1,2,3,4,5,6,7,8,9, 10, 11, 12, 13, or without water. 14, 15, and 16 (according to the IUPAC Group numbering 0079 Organic Ligands format) or Groups IA, IIA, IIIB, IVB, VB, VIIB, VIIB, VIII, 0080. The organic ligands generally serve as linkers or IB, IIB, IIIA, IVA, VA, and VIA (according to the Chemical nodes in the heterocyclic macrocycle-templated assembly of Abstracts Service (CAS) numbering format) of the periodic the molecular building blocks. In general, the organic ligands table and after the Supramolecular metal organic material are linear, branched or cyclic and polyvalent to coordinate heterocyclic macrocycle is formed, the metal coordinated by with metals (including metal ions and metal oxides). Typi the metalated heterocyclic macrocycle is exchanged with a cally, the organic ligands will be linear, branched, monocy second (different) metal selected, for example, from Groups clic, bicyclic or tricyclic and contain at least two coordinating 1,2,3,4,5,6,7,8,9, 10, 11, 12, 13, 14, 15, and 16 (according groups. For example, in one embodiment, the organic ligand to the IUPAC Group numbering format) or Groups IA, IIA, is a linker, containing two metal coordinating groups. In other IIIB, IVB, VB, VIIB, VIIB, VIII, IB, IIB, IIIA, IVA, VA, and embodiments, the organic ligand is a node, containing at least VIA (according to the Chemical Abstracts Service (CAS) 3 metal coordinating groups. In other embodiments, the numbering format) of the periodic table and after the organic ligand is a node, containing at least 4 metal coordi Supramolecular metal organic material heterocyclic macro nating groups. In other embodiments, the organic ligand is a US 2013/018445.6 A1 Jul. 18, 2013 node, containing at least 6 metal coordinating groups. In other wherein the wavy lines represent the attachment point of the embodiments, the organic ligand is a node, containing at least A ring to the remainder of the ligand compound (i.e., at Land 8 metal coordinating groups. In other embodiments, the Ls) of each Substituent arm). organic ligand is a node, containing at least 12 metal coordi I0088. In certain embodiments, A is a six-membered ring nating groups. In other embodiments, the organic ligand is a moiety. In general, the six-membered A ring may be any node, containing at least 24 metal coordinating groups. saturated or unsaturated six-membered carbocyclic or hetero 0081. In one embodiment, the ligand compound corre cyclic ring structure. Cationic forms of the carbocyclic or sponds to Formula (1): heterocyclic A ring are also contemplated; that is, a free electron pair of a carbon or heteroatom may be involved in the R-L-A-L-R), (1) skeletal bonding of the ring system, e.g., in the formation of wherein the ring or in the double bond system of the ring. 0082 A is a bond or a monocyclic ring or polycyclic ring I0089. In one embodiment. A ring is a six-membered car system; bocyclic or heterocyclic ring having the structure: 0083 L and each L is a linker moiety; 0084 n is at least 1; and 0085 R. and each R is independently a functional group capable of coordinately bonding to at least one metalion. I0086. In one exemplary embodiment, the organic ligand corresponds to Formula 1, n is 1, A is a bond, L and L are linkers, and the organic ligand contains two metal coordinat ing groups, R and Rs. 0087. In another exemplary embodiment, n is 1 or 2, A is a monocyclic or polycyclic ring system, L and L are linkers, and the organic ligand contains one R metal coordinating groups and one or two R metal coordinating groups. In wherein general, when A is a ring system, the A ring system may 0090 the atoms defining the ring, A. A. A. A. As and comprise any Saturated or unsaturated carbocyclic or hetero As are independently selected from carbon, nitrogen, oxy cyclic ring structure. The A ring may be monocyclic, or may gen, boron, and sulfur atoms (including cations thereof); be a bicyclic, tricyclic, hexacyclic, or otherwise polycyclic 0091 the A, A, and As ring atoms are substituted with ring system, provided that the polycyclic ring system is the -L-R, and -L-R, ring moieties (as described in connec capable of being substituted in the manner described and tion with Formula (1): illustrated in connection with Formula 1. In one embodiment 0092 A, A, and A are independently-L--R (as pre in which the A ring is a polycyclic ring system, the A ring has viously defined in connection with Formula 1) or any atom or the structure: group of atoms that do not otherwise affect the substituent arms, 0093 the dashed lines represent single or double bonds, or collectively form a conjugated bond system that is unsatur ated to a degree of aromaticity; and 0094 the wavy lines represent the attachment point of the A ring to the remainder of the ligand compound (i.e., at L or Ls of each substituent arm). 0095. In general, the A, A, and A Substituents are selected such that they will not adversely affect other sub stituents on the ligand compound and/or will not affect assembly of the desired ligands and further assembly of the molecular building blocks. Suitable substituents for A. A. and Ace include, for example, one or more of the following chemical moieties: H, OH, OR,-COOH, -COOR, CONH, -NH, -NHR, NRR, SH, -SR, -SOR, —SOH, -SOR, and halo (including F, Cl, Br, and I), O wherein each occurrence of R may be hydrocarbyl or substi tuted hydrocarbyl (e.g., substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubsti tuted araklyl). Alternatively, one or more of A, A, and Age may be -L--R (as previously defined in connection with Formula 1). 0096. In one embodiment, n is 1 or 2 and A is a six membered aromatic ring. Alternatively, the A ring may be a six-membered non-aromatic ring. In one embodiment, for example, the six-membered A ring is selected from benzene, pyridine, pryridinium, pyrimidine, pyrimidinium, triazine, triazinium, pyrylium, boroXine, diborabenzene, and tribora US 2013/018445.6 A1 Jul. 18, 2013

benzene rings. Thus, for example, when n is 1 or 2 the A ring -continued may correspond to one of the following exemplary six-mem- (A) bered rings:

(A1) n N

2

(A8)

c. (A2)

(A9)

(A3) N1SN 2 NN (A10) 21

(A4) N1 NN

-- N 2 N N 2 (A11)

(A5) -- N Ns 4. 2 N

(A6) (A12)

NN I 1S I 21 >, N1 X US 2013/018445.6 A1 Jul. 18, 2013

-continued stituent arm). In one preferred embodiment. A ring is a ben (A13) Zene ring. According to this embodiment, therefore, the A ring has the formula:

N x-y (A14)

B 1 n wherein the wavy lines represent the attachment point of the benzene ring to the remainder of the ligand compound corre sponding to Formula (1) (i.e., at L or L of each Substituent x-y arm). 0099. In one embodiment, the organic ligand corresponds (A15) to Formula 1 and n is 1. In another embodiment, n is 2. In another embodiment, n is 3. In another embodiment, n is 4. In another embodiment, n is at least 6. In another embodiment, n is at least 8. In another embodiment, n is at least 12. In another embodiment, n is at least 24. 0100. The ligand compounds of Formula (1) also possess the L and L linking moieties, which join the R and R Substituents to the A moiety. In each of the ligand compounds described herein, the L and L linking moieties may com wherein the wavy lines represent the attachment point of the prise covalent bonds, coordinate covalent bonds, noncovalent A ring to the remainder of the ligand compound correspond bonds, or a combination thereof. In certain embodiments, L. ing to Formula (1) (i.e., at L or L of each Substituent arm). and/or each L comprise direct chemical bonds. In certain 0097. In one embodiment, n is 1 or 2, and A is a six other embodiments, L and/or each L. may comprise organic membered benzene, boroXine, pyridyl or triazine ring. linking moieties. In still other embodiments, L and each L According to this embodiment, therefore, the A ring is may independently comprise coordinating bonds. selected from: 0101. In general, the dimension, pore size, free volume, and other properties of the molecular building blocks and metal-organic frameworks including the ligands described herein can be correlated to the linker moieties, L and L of the ligand compound. For example, expanded structures can result from expanding the series of linkers (e.g., as a series of phenylene moieties), and the pore size can be reduced by the selection of functional groups on the linkers that point towards the inner cavities of the building blocks. In addition, other functional properties of the resulting building blocks can be selected by the appropriate selection of substituents (e.g., fluorescent or catalytic moieties) on the linking Sub units. I0102) The L and L linking moieties are generally the same and link the R and R. Substituents to the A moiety at the 1 and 3 positions, respectively. 0103 Typically, L is a bond or -(L)-, wherein L is heterocyclene, hydrocarbylene, or substituted hydrocarby lene and m is a positive integer, L is a bond or -(L)-. wherein L is hydrocarbylene or substituted hydrocarbylene and n is a positive integer, with L and L being the same, and n m is a positive integer. In one particular embodiment, Land Ls are each bonds. 2 2 0104. Where L and/or L are -(L)- and -(L)-. respectively, although L and L. may be heterocyclene, hydrocarbylene, or substituted hydrocarbylene, in certain embodiments L and L are Substituted or unsubstituted 0098 wherein the wavy lines represent the attachment alkylene, alkenylene, alkynylene, arylene, or heterocyclene. point of the A ring to the remainder of the ligand compound Where L and L are alkylene or alkenylene, for example, corresponding to Formula (1) (i.e., at L or L of each Sub they may be straight, branched, or cyclic, preferably straight US 2013/018445.6 A1 Jul. 18, 2013 or cyclic. The L and L. moieties may also be alkynyl. Such tuted hydrocarbyl (e.g., substituted or unsubstituted alkyl, as ethynyl. In one preferred embodiment, Land L are -(L) substituted or unsubstituted aryl, or substituted or unsubsti - and -(Las),-, respectively, wherein Land Las are Substi tuted araklyl). tuted or unsubstituted alkylene, alkynyl, substituted or unsub 0111 Although L and L are generally the same, when stituted arylene, or heterocyclene. these moieties are substituted hydrocarbylene they may not 0105. In a particularly preferred embodiment, L and L. necessarily carry the same Substituents on each hydrocarby are each bonds or are -(L)- and -(Las),-, respectively, lene moiety. For instance, L. may be substituted phenylene wherein Land L. correspond to one of the following struc carrying a particular halo Substituent (e.g., F. Cl, Br, and/or I), tures: or a combination thereof, while L. may be substituted phe nylene carrying a different halo substituent (or a different combination of halo substituents), or different substituents - - - - R. F w altogether (e.g., —OH or NH). Thus, in various embodi A ments L1 and Las are independently: w F w A. w F V - - - - as a Xs X6

w wwer - - - - - w

N---Nar iii. ------. ' N N X X

wherein m is a positive integer and each X, Xs, Xs, and X is independently -H, -OH, -OR, -COOH, -COOK, CONH, -NH, -NHR, NRR, -SH, -SR, -SOR, —SOH, -SOR, or halo. In these and other embodiments, Lss may be: wherein Xs X6 0106 the dashed lines represent single or double bonds, or collectively form a conjugated bond system that is unsatur ated to a degree of aromaticity; 0107 the wavy lines represent the attachment point of the iii. L or Las moiety to the A moiety and another L or Las moiety (i.e., when m is 2 or more) or to the A moiety and R. or R, and 0108) each m is a positive integer. wherein m is a positive integer and each X, Xs, Xs, and X is 0109. In another preferred embodiment, L and L are independently -H, -OH, -OR, -COOH, -COOR, each bonds or are -(L)- and -(L)-, respectively, wherein CONH, -NH, -NHR, NRR, SH, -SR, -SOR, L and L are Substituted or unsubstituted arylene; more —SOH, -SOR, or halo. The substituents on a substituted preferably in this embodiment, L and L are substituted or hydrocarbylene Lss moiety may be the same or different from unsubstituted phenylene. those of a substituted or unsubstituted hydrocarbylene L. 0110. Where L and/or each L is substituted hydrocar and/or L. moiety. bylene (e.g., Substituted alkylene or Substituted arylene, more 0112. Where L and L are -(L)- and -(L)-respec preferably substituted phenylene), the substituents may be tively, the number of L and L. repeat units, m, is a positive any of a variety of substituents to impart a desired effect or integer. As noted above, Land L are generally the same, so property to the ligand compound, molecular building block, the number of repeat units, m, for these moieties will be the or the resulting Supramolecular building block or metal-or same. The number of repeat units for Lss, however, may be ganic framework comprising Such ligands and building the same or different than the number of repeat units for the blocks. As noted above, the substituent(s) for the linker moi L and L. moieties. Generally speaking, compounds carry eties may be selected to impart various desired properties, ing more than ten (10) L and/or L. repeat units tend to be Such as magnetic activity, luminescent activity, phosphores less desired, as the Substituent arms can lose rigidity and lack cent activity, fluorescent activity, and catalytic and redox the proper orientation for assembly into larger molecular and activity to the building blocks and assembled structures com molecular building blocks and metal-organic frameworks. prising these components. Exemplary Substituents which Typically, where present, each m is 1 to 10 (e.g., 1, 2, 3, 4, 5, may be found on the substituted alkylene or substituted 6, 7, 8, 9, or 10). In one embodiment, L and L are -(L)- arylene (e.g., Substituted phenylene) moieties of L and L. and -(-)-, respectively, wherein Land L are substituted include, but are not limited to, one or more of the following or unsubstituted phenylene and each m is 1, 2, 3, 4, or 5: more chemical moieties: -OH, - OR, -COOH, -COOR, preferably, each m is 1, 2, or 3. —CONH, -NH, -NHR, NRR, SH, SR, -SOR, 0113. In addition to the A moiety, L and L, the ligand —SOH, -SOR, and halo (including F, Cl, Br, and I), compound corresponding to Formula (1) carries the R and wherein each occurrence of R may be hydrocarbyl or substi R substituents. Generally, the R and R substituents are US 2013/018445.6 A1 Jul. 18, 2013

functional groups capable of coordinately bonding to at least 0118 Metals one metal (including metalions and metal oxides). The func 0119. As discussed above, the metal organic materials of tional groups for R and R are preferably at least bidentate, the present invention comprise molecular building blocks, and may be tridentate, or otherwise polydentate. In one derived from the metal and organic ligands, and cavities embodiment, R and R are bidentate functional groups. enclosed by the molecular building blocks, in which a meta lated heterocyclic macrocycle. Such as a metalated porphyrin, 0114. In particular, the R and R groups are capable of resides. The metals comprised by the molecular building coordinately bonding to at least one metal (including metal blocks and the metals comprised by the metalated heterocy ions and metal oxides) and typically at least two metals clic macrocycles may be the same or different. In one embodi (which may be either the same or different) to form the ment, they are the same. In another embodiment, they are molecular building block. Thus, for example, while the R different. In yet another embodiment, the molecular building and R groups may be initially be a functional group, when blocks comprise organic ligands coordinating two or more combined with metal(s) in the formation of the molecular different metals. building block the R and R groups become coordinating 0120 In general, the organic ligands of the molecular groups with the metal ions or oxides. building blocks can coordinate with metal ions from Groups 0115 Representative functional groups capable of coordi 1,2,3,4,5,6,7,8,9, 10, 11, 12, 13, 14, 15, and 16 (according nately binding to at least one metal include, but are not limited to the IUPAC Group numbering format) or Groups IA, IIA, to, the following: —CO.H. —CSH, NO. —SOH, -Si IIIB, IVB, VB, VIIB, VIIB, VIII, IB, IIB, IIIA, IVA, VA, and (OH), —Ge(OH), —Sn(OH), —Si(SH), —Ge(SH), VIA (according to the Chemical Abstracts Service (CAS) —Sn(SH), —POH, - AsOH, - AsOH, -P(SH). —As numbering format) of the periodic table. This includes, for (SH), —CH(SH), —C(SH), —CH(NH), —C(NH), example, metal ions from the alkali metals, alkaline earth —CH(OH), C(OH), —CH(CN), and –C(CN), —CH metals, transition metals, Lanthanides, Actinides, and other (RSH), C(RSH), —CH(RNH), C(RNH), —CH metals. In order to form building blocks of the desired shape (ROH), C(ROH), —CH(RCN), and C(RCN), and orientation, a metalion is selected having the appropriate wherein each R is independently an alkyl or alkenyl group coordination geometry (e.g., linear, trigonal planar, tetrahe having from 1 to 5 carbon atoms, or an aryl group consisting dral, square planar, trigonal bipyramidal, square pyramidal, of 1 to 2 phenyl rings. Other functional groups capable of octahedral, trigonal prismatic, pentagonal bipyramidal, coordinately binding to at least one metal include, but are not cubic, dodecahedral, hexagonal bipyramidal, icosahedron, limited to, nitrogen donors such as, for example, cyano cuboctahedron, etc.). (—CN), amino, pyrazole, imidazole, pyridine, and functional I0121 The bond angle between the ligands and the metal groups containing Such moieties. See, e.g., Tominaga et al., ion generally dictates the topology of the molecular building Angew. Chem. Int. Ed. 2004, 43,5621-5625. block, while the functional groups on the ligands coordinate with metal ions to form the molecular building block. For 0116. In one preferred embodiment, R and R are car example, in one embodiment the molecular building block is boxylic acid (-COH) groups. According to this embodi triangular and the metal ions are transition metals. In one ment, when the organic ligand is combined with one or more particular embodiment, the molecular building block metal metals during the formation of a molecular building block, ions are selected from first row transition metals. In another the carboxylic acid moieties become carboxylate moieties particular embodiment, the molecular building block metal which coordinately bond with two metals in the following ions are selected from second row transition metals. In (bidentate) manner: another particular embodiment, the molecular building block metal ions are selected from third row transition metals. In another embodiment, molecular building block metalions are M MD selected from the group consisting of Ag", Al", Au", Cui", Cu", Fe?", Fe", Hg", Li", Mn, Mn, Nd", Ni", Ni", Pd, Pd, Pt", Pt", T', Yb and Yb", along with the M-- C )-- (-( pi corresponding metal salt counterion (if present). In one pre ferred embodiment, molecular building block metal ions are the same and are selected from the group consisting of Ag", wherein n is at least 1, M and M and each M, and M, are Au", Cu?", Cu", Fe?", Fe", Hg", Li", Mn", Mn?", Ni?", metal ions (including metal oxides) and the dashed lines Ni, Pd*, Pd, Pt", and Pt", along with the corresponding represent coordination bonds, with other coordination being metal salt counterion (if present). In another preferred possible with the metals and other moieties not specifically embodiment, molecular building block metalions are copper, illustrated (e.g., between M and M, between M and M. chromium, iron or Zinc ions along with the corresponding and/or between M. M. M., and/or M, an other moieties metal salt counterion (if present). Suitable counterions (for example, additional ligand compounds)), and the A moi include, for example, F, Cl, Br, I, CIO, CIO, CIO, ety, Land L are as defined in connection with Formula (1) CIO, OH, NO, NO, SO, SO, PO, and CO. above. I0122. In another embodiment, the molecular building 0117. In one preferred embodiment, the organic ligand block has square pyramidal geometry and the metal ions are corresponds to Formula (1) and contains at least carboxylate transition metals. For example, in one such embodiment, the moieties, at least two heteroaromatic amine moieties, or at molecular building block metal ions are first row transition least two phenoxy moieties. Alternatively, the organic ligands metals. In another Such embodiment, the molecular building may contain combinations of at least one carboxylate moiety, block metal ions the metal ions are second row transition at least one heteroaromatic amine moiety, and/or at least one metals. In another Such embodiment, the molecular building phenoxy moiety. block metal ions are third row transition metals. In another US 2013/018445.6 A1 Jul. 18, 2013

Such embodiment, the molecular building block metal ions 0128 Porphyrins are selected from the group consisting of Al", Bi", Bi", I0129. The porphyrins employed as structure directing Bi"; Cd?", Cu?", Cut, Co, Co?", Cr, Eu?", Eu", Fe", agents in the process of the present invention may be any of a Fe", Gd", Mo', Ni2+, Ni", Ost, Os?", Pt?", Pt", Re", wide range of porphyrins, including metalated porphyrins, Re?", Rh?", Rh", Ru", Ru?", Sm", Sm", Te", Teó", Te7", known in the art. In one embodiment, the porphyrin is a W",Y", and Zn", along with the corresponding metal salt meso-porphyrin, including metalated meso-porphyrins. counterion (if present). In another Such embodiment, the molecular building block metal ions are the same and are 0.130. In one embodiment, the porphyrin complex is a selected from the group consisting of Bi", Bi", Bi"; Cd", porphyrin corresponding to Formula P-1: Cu?", Cut, Co", Co?", Cr", Fe", Fe", Mo", Ni2", Ni", Pt?", Pt", Re, Re?", Rh?", Rht, Ru, Ru?", W, Y, and Zn", along with the corresponding metal salt counterion (if present). Suitable counterions include, for example, F, Cl, Br, I, CIO, CIO, CIO, CIO, OH, NO, NO, SO, SO, PO, and CO. 0123. Other suitable coordinating metals include those described in U.S. Pat. No. 5,648,508 (hereby incorporated by reference herein in its entirety). In addition to the metal ions and metal salts described above, other metallic and metal-like compounds may be used. Such as Sulfates, phosphates, and other complex counterion metal salts of the main- and Sub group metals of the periodic table of the elements. Metal oxides, mixed metal oxides, with or without a defined stoichi ometry may also be employed. 0.124. It will be understood that all metal ions in a given molecular building block can be in the same transition state or in more than one transition state. In some instances, for example, a counterion may be present to balance the charge. wherein M is present or absent and, when present, is H2 or a The counterions themselves may, or may not, be coordinated coordinated metal, and each Z, Z, Z, Z, Zs and Z is to the metal. Suitable counterions are described elsewhere independently selected from the group consisting of hydro herein. gen, hydrocarbyl, Substituted hydrocarbyl, heterocyclo, 0125. In general, the heterocyclic macrocycles, in general, and the porphyrins, in particular, can coordinate with metal alkoxy and amino. In one embodiment, Z, Z, Z and Zs are ions from Groups 1,2,3,4,5,6,7,8,9, 10, 11, 12, 13, 14, 15, hydrogen and Z and Z are independently hydrogen, hydro and 16 (according to the IUPAC Group numbering format) or carbyl, substituted hydrocarbyl, heterocyclo, alkoxy or Groups IA, IIA, IIIB, IVB, VB, VIIB, VIIB, VIII, IB, IIB, amino. For example, in one embodiment, Z.Z.Z. and Zs are IIIA, IVA, VA, and VIA (according to the Chemical Abstracts hydrogen and Z and Z are independently hydrocarbyl, Sub Service (CAS) numbering format) of the periodic table. This stituted hydrocarbyl, or heterocyclo. By way of further includes, for example, metal ions from the alkali metals, example, in one embodiment, Z, Z, Z and Zs are hydrogen alkaline earth metals, transition metals, Lanthanides, and Z and Z are the same and are hydrocarbyl, Substituted Actinides, and other metals. In one embodiment, the metal hydrocarbyl, or heterocyclo. By way of further example, in atom coordinated by the metalated heterocyclic macrocycle one embodiment, Z, Z, Z and Zs are hydrogen and Z and is preferably a transition metal. For example, the metalated heterocyclic macrocycle may coordinate any of the 30 metals Z are different and are hydrocarbyl, substituted hydrocarbyl, in the 3d, 4d and 5d transition metal series of the Periodic or heterocyclo. By way of further example, in one embodi Table of the Elements, including the 3d series that includes ment, Z, Z, Z and Zs are hydrogen and Z and Z are the Sc, Ti, V. Cr, Mn, Fe, Co, Ni, Cu, and Zn; the 4d series that same and are heterocyclo. By way of further example, in one includes Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag and Cd; and the 5d embodiment, Z, Z, Zand Z are hydrogen and Z and Z are series that includes Lu, Hf, Ta, W. Re, Os, Ir, Pt, Au and Hg. the different and are optionally substituted aryl. By way of In some embodiments, the metal is from the 3d series. In some further example, in one embodiment, Z, Z, Z and Z are embodiments, the metal is selected from Co, Cd, Mn, Zn, Fe, hydrogen, Z is optionally Substituted aryl, e.g., optionally and Ni. Substituted phenyl, and Z is optionally Substituted aryl, e.g., 0126 Heterocyclic Macrocycles optionally Substituted phenyl, and the porphyrin is a chiral 0127. The heterocyclic macrocycles employed as struc porphyrin. By way of further example, in one embodiment, ture directing agents in the process of the present invention Z, Z, Z and Zs are hydrogen, Z is optionally Substituted may be any of a wide range of heteroatom-containing mac heterocyclo, e.g., optionally substituted pyridyl, and Z is rocycles, and metalated heterocyclic macrocycles, known in optionally Substituted heterocyclo, e.g., optionally Substi the art. In one embodiment, the metalated heterocyclic mac rocycle is a meso-porphyrin, including metalated meso-por tuted pyridyl, and the porphyrin is a chiral porphyrin. By way phyrins, a meso-porphyrazin, including metalated meso-por of further example, in one embodiment, Z, Z, Z and Zs are phyrazins, a meso-chlorin, including metalated meso hydrogen, Z is optionally Substituted aryl or heterocyclo, Ze , a meso-corrin, including metalated meso-, is optionally Substituted aryl or heterocyclo, and the porphy and meso-porphyrinogen, including metalated meso-porphy rin has D-symmetry. In each of the foregoing embodiments, rinogens. M may be a metal selected from Co, Cd, Mn, Zn, Fe, and Ni. US 2013/018445.6 A1 Jul. 18, 2013

0131. In one exemplary embodiment, a preferred embodi wherein ment, Z is

(Z10), SS 2 O >, HET-(Zo), denotes the point of attachment of Z to the porphyrin, HET is a 5- or 6-membered heterocyclo, n is 0-5, each Zo is hydro carbyl, substituted hydrocarbyl, alkoxy or amino. For wherein example, in one such embodiment, HET is a 5- or 6-mem bered heteroaromatic, n is 0 or 1, and Zo is hydrocarbyl, substituted hydrocarbyl, alkoxy or amino. By way of further example, in one Such embodiment, HET is a pyridyl, pyrim idinyl, pyrazinyl, pyrrolyl, imidazolyl, or oxazolyl, n is 0 or 1, and Zo is hydrocarbyl, Substituted hydrocarbyl, alkoxy or amino. By way of further example, in one such embodiment, denotes the point of attachment of Z to the porphyrin, HET is Z is selected from the group consisting of a 5- or 6-membered heterocyclo, n is 0-5, each Zo is hydro carbyl, substituted hydrocarbyl, alkoxy or amino. For example, in one such embodiment, HET is a 5- or 6-mem bered heteroaromatic, n is 0 or 1, and Zo is hydrocarbyl, w H W H substituted hydrocarbyl, alkoxy or amino. By way of further example, in one such embodiment, HET is a pyridyl, pyrim idinyl, pyrazinyl, pyrrolyl, imidazolyl, or oxazolyl, n is 0 or 1, and Zo is hydrocarbyl, Substituted hydrocarbyl, alkoxy or amino. By way of further example, in one such embodiment, Z is selected from the group consisting of

and s

wherein

H-N O Y=o denotes the point of attachment of Z to the porphyrin. In each of the foregoing embodiments, M may be a metal selected ON, from Co, Cd, Mn, Zn, Fe, and Ni. 0.132. In one exemplary embodiment, a preferred embodi ment, Z is wherein

(Z10), S/S O -- 2 xiii- 10)n denotes the point of attachment of Z to the porphyrin. In each of the foregoing embodiments, M may be a metal selected from Co, Cd, Mn, Zn, Fe, and Ni. US 2013/018445.6 A1 Jul. 18, 2013 13

0.133 Exemplary metalated porphyrins include the fol- -continued lowing porphyrins, designated P11, P12, P13, P14, P15, P16, P13

P17 and P18: US 2013/018445.6 A1 Jul. 18, 2013 14

-continued P16, or P17 and M is Co(II). In another such embodiment, the P16 porphyrin is a metalated porphyrin corresponding instructure to P11, P12, P13, P14, P15, P16, or P17 and Mis Cd, Mn, Zn, Fe, or Ni. I0134 Porphyrazins 0.135 The porphyrazins employed as structure directing agents in the process of the present invention may be any of a wide range of porphyrazins, including metalated por phyrazins, known in the art. In one embodiment, the porphy rin is a meso-porphyrazin, including metalated meso-por phyrazins. 0.136. In one embodiment, the porphyrin complex is a porphyrazin corresponding to Formula P-21:

P-21 Z2 Z1 Z3 z-Z NZ Na Z4 eN N / Z-N N/ N-Z P17 \ / N N

ZN s | 7 NZ. Z2 y Z3

wherein M is present or absent and, when present, is H or a coordinated metal, and each Z, Z2, Z, Z, Zs and Z is independently selected from the group consisting of hydro gen, hydrocarbyl, Substituted hydrocarbyl, heterocyclo, alkoxy and amino. In one embodiment, Z, Z, Z and Zs are hydrogen and Z and Z are independently hydrogen, hydro carbyl, substituted hydrocarbyl, heterocyclo, alkoxy or amino. For example, in one embodiment, Z.Z.Z. and Zs are hydrogen and Z and Z are independently hydrocarbyl, Sub stituted hydrocarbyl, or heterocyclo. By way of further example, in one embodiment, Z, Z, Z and Zs are hydrogen and Z and Z are the same and are hydrocarbyl, Substituted hydrocarbyl, or heterocyclo. By way of further example, in one embodiment, Z, Z, Z and Zs are hydrogen and Z and Zare different and are hydrocarbyl, substituted hydrocarbyl, or heterocyclo. By way of further example, in one embodi ment, Z, Z, Z and Zs are hydrogen and Z and Z are the same and are heterocyclo. By way of further example, in one embodiment, Z, Z, Zand Z are hydrogen and Z and Z are the different and are optionally substituted aryl. By way of further example, in one embodiment, Z, Z, Z and Zs are hydrogen, Z is optionally substituted aryl, e.g., optionally Substituted phenyl, and Z is optionally Substituted aryl, e.g., optionally Substituted phenyl, and the porphyrazin is a chiral porphyrazin. By way of further example, in one embodiment, Z, Z, Z and Zs are hydrogen, Z is optionally Substituted heterocyclo, e.g., optionally substituted pyridyl, and Z is optionally Substituted heterocyclo, e.g., optionally Substi tuted pyridyl, and the porphyrazin is a chiral porphyrazin. By way of further example, in one embodiment, Z, ZZ and Zs are hydrogen, Z is optionally substituted aryl or heterocyclo, Z is optionally substituted aryl or heterocyclo, and the por phyrazin has D-symmetry. In each of the foregoing embodi In one Such embodiment, the porphyrin is a metalated por ments, M may be a metal selected from Co, Cd, Mn, Zn, Fe, phyrin corresponding in structure to P11, P12, P13, P14. P15, and Ni. US 2013/018445.6 A1 Jul. 18, 2013

0.137 In one exemplary embodiment, a preferred embodi wherein ment, Z is

(Z10), SS 2 O >, HET-(Zo), denotes the point of attachment of Z to the porphyrazin, HET is a 5- or 6-membered heterocyclo, n is 0-5, each Zo is hydrocarbyl, substituted hydrocarbyl, alkoxy or amino. For wherein example, in one such embodiment, HET is a 5- or 6-mem bered heteroaromatic, n is 0 or 1, and Zo is hydrocarbyl, substituted hydrocarbyl, alkoxy or amino. By way of further example, in one Such embodiment, HET is a pyridyl, pyrim idinyl, pyrazinyl, pyrrolyl, imidazolyl, or oxazolyl, n is 0 or 1, and Zo is hydrocarbyl, Substituted hydrocarbyl, alkoxy or amino. By way of further example, in one such embodiment, denotes the point of attachment of Z to the porphyrazin, HET Z is selected from the group consisting of is a 5- or 6-membered heterocyclo, n is 0-5, each Zo is hydrocarbyl, substituted hydrocarbyl, alkoxy or amino. For example, in one such embodiment, HET is a 5- or 6-mem bered heteroaromatic, n is 0 or 1, and Zo is hydrocarbyl, w H w H substituted hydrocarbyl, alkoxy or amino. By way of further example, in one such embodiment, HET is a pyridyl, pyrim idinyl, pyrazinyl, pyrrolyl, imidazolyl, or oxazolyl, n is 0 or 1, and Zo is hydrocarbyl, Substituted hydrocarbyl, alkoxy or amino. By way of further example, in one such embodiment, Z is selected from the group consisting of

and s

wherein

H-N O Y=o denotes the point of attachment of Z to the porphyrazin. In each of the foregoing embodiments, M may be a metal ON, selected from Co, Cd, Mn, Zn, Fe, and Ni. 0.138. In one exemplary embodiment, a preferred embodi ment, Z is wherein

(Z10), S/S O -- 2 xiii- 10)n denotes the point of attachment of Z to the porphyrazin. In each of the foregoing embodiments, M may be a metal selected from Co, Cd, Mn, Zn, Fe, and Ni. US 2013/018445.6 A1 Jul. 18, 2013

0139 Chlorins 0142. In one exemplary embodiment, a preferred embodi 0140. The chlorins employed as structure directing agents ment, Z is in the process of the present invention may be any of a wide range of chlorins, including metalated chlorins, known in the (Z10), art. In one embodiment, the chlorin is a meso-chlorin, includ SA ing metalated meso-chlorins. O 0141. In one embodiment, the chlorin complex is a chlorin 21 >, HET-(Zo), corresponding to Formula P-31:

wherein

denotes the point of attachment of Z to the chlorin, HET is a 5- or 6-membered heterocyclo, n is 0-5, each Zo is hydrocar byl, substituted hydrocarbyl, alkoxy or amino. For example, in one such embodiment, HET is a 5- or 6-membered het eroaromatic, n is 0 or 1, and Zo is hydrocarbyl, Substituted hydrocarbyl, alkoxy oramino. By way of further example, in one such embodiment, HET is a pyridyl, pyrimidinyl, pyrazi nyl, pyrrolyl, imidazolyl, or oxazolyl, n is 0 or 1, and Zo is hydrocarbyl, substituted hydrocarbyl, alkoxy or amino. By way of further example, in one such embodiment, Z is wherein M is present or absent and, when present, is H2 or a selected from the group consisting of coordinated metal, and each Z, Z2, Z, Z, Zs and Z is independently selected from the group consisting of hydro gen, hydrocarbyl, Substituted hydrocarbyl, heterocyclo, alkoxy and amino. In one embodiment, Z, Z, Z and Zs are hydrogen and Z and Z are independently hydrogen, hydro and s carbyl, substituted hydrocarbyl, heterocyclo, alkoxy or amino. For example, in one embodiment, ZZZ and Zs are hydrogen and Z and Z are independently hydrocarbyl, Sub stituted hydrocarbyl, or heterocyclo. By way of further example, in one embodiment, Z, Z, Z and Zs are hydrogen and Z and Z are the same and are hydrocarbyl, Substituted hydrocarbyl, or heterocyclo. By way of further example, in wherein one embodiment, Z, Z, Z and Zs are hydrogen and Z and Zare different and are hydrocarbyl, substituted hydrocarbyl, or heterocyclo. By way of further example, in one embodi ment, Z2, Z, Z and Zs are hydrogen and Z and Z are the same and are heterocyclo. By way of further example, in one embodiment, Z, Z, Zand Z are hydrogen and Z and Z are the different and are optionally substituted aryl. By way of further example, in one embodiment, Z, Z, Z and Z are denotes the point of attachment of Z to the chlorin. In each of hydrogen, Z is optionally Substituted aryl, e.g., optionally the foregoing embodiments, M may be a metal selected from Substituted phenyl, and Z is optionally Substituted aryl, e.g., Co, Cd, Mn, Zn, Fe, and Ni. optionally substituted phenyl, and the chlorin is a chiral chlo 0143. In one exemplary embodiment, a preferred embodi rin. By way of further example, in one embodiment, Z.Z.Z. ment, Z is and Zs are hydrogen, Z is optionally Substituted heterocyclo, e.g., optionally Substituted pyridyl, and Z is optionally Sub (Z10), or stituted heterocyclo, e.g., optionally Substituted pyridyl, and Ás HET-(Zo), the chlorin is a chiral chlorin. By way of further example, in one embodiment, ZZZ and Zs are hydrogen, Z is option ally Substituted aryl or heterocyclo, Z is optionally Substi lul 54. tuted aryl or heterocyclo, and the chlorin has D-symmetry. In each of the foregoing embodiments, M may be a metal selected from Co, Cd, Mn, Zn, Fe, and Ni. US 2013/018445.6 A1 Jul. 18, 2013

wherein 0144 Corrins 0145 The corrins employed as structure directing agents in the process of the present invention may be any of a wide range of corrins, including metalated corrins, known in the art. In one embodiment, the corrin is a meso-corrin, including metalated meso-corrins. 0146 In one embodiment, the corrin complex is a corrin denotes the point of attachment of Z to the chlorin, HET is a corresponding to Formula P-41: 5- or 6-membered heterocyclo, n is 0-5, each Zo is hydrocar byl, substituted hydrocarbyl, alkoxy or amino. For example, in one such embodiment, HET is a 5- or 6-membered het eroaromatic, n is 0 or 1, and Zo is hydrocarbyl, Substituted hydrocarbyl, alkoxy oramino. By way of further example, in one such embodiment, HET is a pyridyl, pyrimidinyl, pyrazi nyl, pyrrolyl, imidazolyl, or oxazolyl, n is 0 or 1, and Zo is hydrocarbyl, substituted hydrocarbyl, alkoxy or amino. By way of further example, in one such embodiment, Z is selected from the group consisting of

wherein M is present or absent and, when present, is H2 or a coordinated metal, and each Z, Z2, Z, Z, Zs and Z is independently selected from the group consisting of hydro gen, hydrocarbyl, Substituted hydrocarbyl, heterocyclo, alkoxy and amino. In one embodiment, Z, Z, Z and Zs are hydrogen and Z and Z are independently hydrogen, hydro carbyl, substituted hydrocarbyl, heterocyclo, alkoxy or amino. For example, in one embodiment, Z.Z.Z. and Zs are hydrogen and Z and Z are independently hydrocarbyl, Sub stituted hydrocarbyl, or heterocyclo. By way of further example, in one embodiment, Z, Z, Z and Zs are hydrogen and Z and Z are the same and are hydrocarbyl, Substituted hydrocarbyl, or heterocyclo. By way of further example, in one embodiment, Z, Z, Z and Zs are hydrogen and Z and Zare different and are hydrocarbyl, substituted hydrocarbyl, or heterocyclo. By way of further example, in one embodi ment, Z2, Z, Z and Zs are hydrogen and Z and Z are the same and are heterocyclo. By way of further example, in one embodiment, Z, Z, Zand Z are hydrogen and Z and Z are the different and are optionally substituted aryl. By way of further example, in one embodiment, Z, Z, Z and Z are hydrogen, Z is optionally Substituted aryl, e.g., optionally Substituted phenyl, and Z is optionally Substituted aryl, e.g., optionally substituted phenyl, and the corrin is a chiral corrin. wherein By way of further example, in one embodiment, Z, Z, Za and Zs are hydrogen, Z is optionally Substituted heterocyclo, e.g., optionally Substituted pyridyl, and Z is optionally Sub stituted heterocyclo, e.g., optionally Substituted pyridyl, and the corrin is a chiral corrin. By way of further example, in one embodiment, Z, Z, Z and Zs are hydrogen, Z is optionally substituted aryl or heterocyclo, Z is optionally substituted denotes the point of attachment of Z to the chlorin. In each of aryl or heterocyclo, and the corrin has D-symmetry. In each the foregoing embodiments, M may be a metal selected from of the foregoing embodiments, M may be a metal selected Co, Cd, Mn, Zn, Fe, and Ni. from Co, Cd, Mn, Zn, Fe, and Ni. US 2013/018445.6 A1 Jul. 18, 2013

0147 In one exemplary embodiment, a preferred embodi wherein ment, Z is

(Z10), or S/S HET-(Zo) 21 %. denotes the point of attachment of Z to the corrin, HET is a 5- or 6-membered heterocyclo, n is 0-5, each Zo is hydrocar byl, substituted hydrocarbyl, alkoxy or amino. For example, wherein in one such embodiment, HET is a 5- or 6-membered het eroaromatic, n is 0 or 1, and Zo is hydrocarbyl, Substituted hydrocarbyl, alkoxy oramino. By way of further example, in one such embodiment, HET is a pyridyl, pyrimidinyl, pyrazi nyl, pyrrolyl, imidazolyl, or oxazolyl, n is 0 or 1, and Zo is hydrocarbyl, substituted hydrocarbyl, alkoxy or amino. By way of further example, in one such embodiment, Z is selected from the group consisting of denotes the point of attachment of Z to the corrin, HET is a 5- or 6-membered heterocyclo, n is 0-5, each Zo is hydrocar byl, substituted hydrocarbyl, alkoxy or amino. For example, in one such embodiment, HET is a 5- or 6-membered het eroaromatic, n is 0 or 1, and Zo is hydrocarbyl, Substituted hydrocarbyl, alkoxy oramino. By way of further example, in one such embodiment, HET is a pyridyl, pyrimidinyl, pyrazi nyl, pyrrolyl, imidazolyl, or oxazolyl, n is 0 or 1, and Zo is hydrocarbyl, substituted hydrocarbyl, alkoxy or amino. By way of further example, in one such embodiment, Z is selected from the group consisting of

and s

wherein

denotes the point of attachment of Z to the corrin. In each of the foregoing embodiments, M may be a metal selected from Co, Cd, Mn, Zn, Fe, and Ni. 0148. In one exemplary embodiment, a preferred embodi ment, Z is wherein

(Z10), or luS/S 7%.HET-(Zo) denotes the point of attachment of Z to the corrin. In each of the foregoing embodiments, M may be a metal selected from Co, Cd, Mn, Zn, Fe, and Ni. US 2013/018445.6 A1 Jul. 18, 2013

0149 0152. In one exemplary embodiment, a preferred embodi 0150. The porphyrinogens employed as structure direct ment, Z is ing agents in the process of the present invention may be any of a wide range of porphyrinogens, including metalated por (Z10), phyrinogens, known in the art. In one embodiment, the por phyrinogen is a meso-porphyrinogen, including metalated meso-porphyrinogens. r21 >, HET-(Zo) 0151. In one embodiment, the porphyrinogen complex is a O porphyrinogen corresponding to Formula P-51: wherein P-51 Z2 Z Z3

Zs Z4

Z6 Z6 denotes the point of attachment of Z to the porphyrinogen, HET is a 5- or 6-membered heterocyclo, n is 0-5, each Zo is hydrocarbyl, substituted hydrocarbyl, alkoxy or amino. For Z Cy Zs example, in one such embodiment, HET is a 5- or 6-mem bered heteroaromatic, n is 0 or 1, and Zo is hydrocarbyl, substituted hydrocarbyl, alkoxy or amino. By way of further Z2 Z Z3 example, in one Such embodiment, HET is a pyridyl, pyrim idinyl, pyrazinyl, pyrrolyl, imidazolyl, or oxazolyl, n is 0 or 1, and Zo is hydrocarbyl, Substituted hydrocarbyl, alkoxy or amino. By way of further example, in one such embodiment, wherein M is present or absent and, when present, is H or a Z is selected from the group consisting of coordinated metal, and each Z, Z, Z, Z, Zs and Z is independently selected from the group consisting of hydro gen, hydrocarbyl, Substituted hydrocarbyl, heterocyclo, alkoxy and amino. In one embodiment, Z, Z, Z and Zs are hydrogen and Z and Z are independently hydrogen, hydro carbyl, substituted hydrocarbyl, heterocyclo, alkoxy or amino. For example, in one embodiment, ZZZ and Zs are hydrogen and Z and Z are independently hydrocarbyl, Sub stituted hydrocarbyl, or heterocyclo. By way of further example, in one embodiment, Z, Z, Z and Zs are hydrogen and s and Z and Z are the same and are hydrocarbyl, Substituted hydrocarbyl, or heterocyclo. By way of further example, in one embodiment, Z, Z, Z and Zs are hydrogen and Z and wherein Z are different and are hydrocarbyl, substituted hydrocarbyl, or heterocyclo. By way of further example, in one embodi ment, Z2, Z, Z and Zs are hydrogen and Z and Z are the same and are heterocyclo. By way of further example, in one embodiment, Z.Z.Z. and Zs are hydrogen and Z and Z are the different and are optionally substituted aryl. By way of further example, in one embodiment, Z, Z, Z and Zs are denotes the point of attachment of Z to the porphyrinogen. In hydrogen, Z is optionally substituted aryl, e.g., optionally each of the foregoing embodiments, M may be a metal Substituted phenyl, and Z is optionally Substituted aryl, e.g., selected from Co, Cd, Mn, Zn, Fe, and Ni. optionally Substituted phenyl, and the porphyrinogen is a 0153. In one exemplary embodiment, a preferred embodi chiral porphyrinogen. By way of further example, in one ment, Z is embodiment, Z, Z, Z and Zs are hydrogen, Z is optionally Substituted heterocyclo, e.g., optionally substituted pyridyl, and Z is optionally Substituted heterocyclo, e.g., optionally (Z10), Substituted pyridyl, and the porphyrinogen is a chiral porphy rinogen. By way of further example, in one embodiment, Z. ZZ and Zs are hydrogen, Z is optionally substituted aryl or r heterocyclo, Z is optionally Substituted aryl or heterocyclo, and the porphyrinogen has D-symmetry. In each of the fore 21 O x-r going embodiments, M may be a metal selected from Co, Cd, Mn., Zn, Fe, and Ni. US 2013/018445.6 A1 Jul. 18, 2013 20 wherein 0154 Supramolecular Metal Organic Material 0155 The organic ligands, metals and heterocyclic mac rocycles may be combined to formany of a range of molecu lar building blocks. Exemplary molecular building blocks include those shown in FIG. 1. 0156 Examples of this new class of material, porph?a MOMs, were prepared solvothermally and all exhibit cage-containing structures that are not afforded if synthesis is denotes the point of attachment of Z to the porphyrinogen, attempted under the same conditions but in the absence of HET is a 5- or 6-membered heterocyclo, n is 0-5, each Zo is porphyrin. Several of the new porphi(a)MOMs exhibit struc hydrocarbyl, substituted hydrocarbyl, alkoxy or amino. For tures in which the porphyrin is accessible via micropores and example, in one such embodiment, HET is a 5- or 6-mem they could therefore represent a new paradigm for biomimetic bered heteroaromatic, n is 0 or 1, and Zo is hydrocarbyl, and industrial chemistry since they inherently combine the substituted hydrocarbyl, alkoxy or amino. By way of further advantages of homogeneous catalysis (high reactivity/turn example, in one such embodiment, HET is a pyridyl, pyrim over rate) and heterogeneous catalysis (recycling of catalyst, idinyl, pyrazinyl, pyrrolyl, imidazolyl, or oxazolyl, n is 0 or 1, facile isolation of product) within a single catalytic system. and Zo is hydrocarbyl, Substituted hydrocarbyl, alkoxy or The porph(a)MOMs also exhibit variable loading of metal amino. By way of further example, in one such embodiment, loporphyrin because the template effect can occur even iflow Z is selected from the group consisting of amounts of porphyrin are used during synthesis and the resulting cages are not fully occupied.

0157 Although the proof-of-concept catalytic studies we report are based upon oxidation catalysis, these are by no means the only catalytic processes that porphoMOMs might effect. In particular porph(a)MOMs should also enable pho tocatalytic reactions that are known to catalysed by metal loporphyrins. Molecular recognition and self-assembly may be used with reactive species in order to pre-organize a system for a chemical reaction (to form one or more covalent bonds). It may be considered a special case of supramolecular cataly sis. Since TMPyP has the appropriate symmetry and size to fit the cuboctahedral cage of HKUST-1, we have investigated whether it might template new variants of HKUST-1. Reac tion of M(II)C1 (M=Mn, Fe and Co) with BTC and TMPyP in DMF and HO at 85°C. for 12 h afforded dark cubic crystals of MTMPyP(a)HKUST-1-M that adopt space group Fm-3m with a 26.5985(17) A, 26.5985(17) A and 26.4301 (11) A for M-Mn, Fe and Co, respectively. Reaction of Ni(OAC), with BTC and TMPyP under the same conditions afforded red octahedral crystals of NiTMPyP(a)HKUST-1'- Ni, a structure with the same space group and tho topology as HKUST-1 but with a 27.478(2) A. The disordered building blocks in NiTMPyP(a)HKUST-1'-Ni are modeled to be a combination of dimetallic M(HO)(carboxylate) and monometallic M(carboxylate)al 4-connected nodes. Mg(OAC) afforded a powder with the same PXRD pattern as NiTMPyP(a)HKUST-1'-Ni but single crystals could not be obtained under the synthesis conditions used (see Supplemen tal information for full details). The porphyrin molecules in these five porphi(a)MOMs are statistically disordered because of the cage symmetry (with the exception of central metal atoms) but the porphyrin planes are clearly resolvable as the Da, symmetry of the porphyrin's core is a subgroup of the cage symmetry and the core is located on the symmetry plane wherein and axes. Variation in the reaction conditions led to porphyrin loading between 12% and 88% as determined by site occu pancy refinement of the metal atom and UV spectroscopy. Notably, the same reactions conducted under the same con ditions but in the absence of porphyrinyielded different prod -- uctS. 0158 We assessed the catalytic activity of FeTMPyP(a)HKUST-1-Fe (50% loading, experimentally denotes the point of attachment of Z to the porphyrinogen. In measured surface area of 423 m/g) and observed that it each of the foregoing embodiments, M may be a metal catalyses size selective olefin oxidation, a classic catalysis selected from Co, Cd, Mn, Zn, Fe, and Ni. reaction of enzymes.” The conversion of styrene (4.2 US 2013/018445.6 A1 Jul. 18, 2013

Ax7.0 A cross-section) reached -85% (turnover frequency Cd-porph?a MOM-1. Benzaldehyde, styrene oxide and (TOF)=269 h-1) after 10hrs, compared to conversion of only 1-phenylethanone were the major products with 57%, 21% ~35% for an equivalent amount of FeTMPyP in solution. and 19% selectivity, respectively. The filtrant can be recycled Styrene oxide and benzaldehyde were identified as the major and even after four 10 hr cycles we observed >55% conver products (30% and 57%, respectively). This is consistent with sion of styrene. Porph?a MOM-4 crystallizes in the mono selectivity previously reported by Maurya. In contrast, clinic space group P2/c with a 17.245(5) A: b=17.025(5) A: trans-stilbene (4.2 Ax11.4. A cross-section) was only ~40% c=45.462(11) A; B=106.981 (9); V=12766(6) A. There are converted under the same conditions (TOF=126 h-1) with two different building blocks in the structure, Zn(O)(COO) trans-stilbene oxide being the major product (70% selectiv ity), compared to conversion of -34% for FeTMPyP in solu s' and Zn (O)(COO), which can be simplified as 6- and tion. The conversion of triphenylethylene (9.0 Ax11.4. A 5-connected nodes that connect BPDA ligands into a 2D net cross-section) by FeTMPyP(a)HKUST-1-Fe was <5% that exhibits 2D to 3D parallel interpenetration. Metallopor (TOF=15 h") under the same conditions whereas FeTMPyP phyrins are located within the interlayers of two interpen in solution exhibited ~14% conversion with diphenylmetha etrating nets with adjacent porphyrins oriented face-to-face none and benzaldehyde being the major products. These fashionata distance of ~7.2 A. Removal of solvent molecules observations are consistent with the oxidation reaction occur would create an accessible free volume of 5017.9A or 39.3% ring in the cages of FeTMPyP(a)HKUST-1-Fe since the pore of the volume of the unit cell. Porphi(a)MOM-5 crystallizes in (-9 Ax9 A) in MTMPyP(a)HKUST-1-M is the window of the the orthorhombic space group=Cmcm with a 20.525(15) A: cuboctahedral cages. The reaction solutions were filtered b=21.985(17)A; c=36.043(13) A:V=16263(22) A3. It exhib after the catalytic reaction. The filtrate showed no detectable its a pcu net that is based upon 6-connected Zn4(COO)s. metalloporphyrin species via UV whereas the filtrant was clusters. As shown in FIG. 6, the metalloporphyrin molecules recycled and even after seven 10 hr cycles we observed >55% are located in every other cavity of the pcu net. It... It stacking conversion of Styrene. interactions between naphthalene moieties and metallopor 0159 HKUST-1 type nets are clearly well-suited to serve phyrins means that metalloporphyrins are ordered from a as platforms for porpha)MOMs but it is unlikely that they are crystallographic perspective and calculations indicate that the only MOMs suitable for porphyrin encapsulation or that 34.5% of the volume of the unit cell is accessible. they will offer optimal performance. We therefore explored 0160 To summarize, the templated porph(a)MOMs whether or not TMPyP might serve as a template for MOM described herein represent a general class of compounds that structures with novel cage-containing topologies. Template addresses these problems as follows: the metalloporphyrin directed synthesis has been widely used in the context of (or other metalated heterocyclic macrocycle described herein zeolite' and mesoporous material synthesis' and it has also catalyst is trapped in a pocket that prevents or slows down its been used in MOMs, including upon HKUST-1-Cu. Five decomposition; the high porosity of MOMs means that a large novel crystalline porph?a MOMs (porph?a MOM-1 to number of catalyst sites are exposed to solution and reaction porph?a MOM-5) were indeed isolated. Cda (BTC) (HO) 3CdTMPyP-4C1, porph(a)MOM-1, ZnO(BPDA), rates are therefore relatively high; the use of porphyrins (and -ZnTMPyP (BPDA=4,4'-biphenyldicarboxylic), other metalated heterocyclic macrocycles described herein) as templates enables the creation of novel MOMs that exhibit porpha MOM-4, and Zn (1,4-NPD):ZnTMPyP (1,4- a cavity that is templated by the porphyrin (or other hetero NPD=1.4-naphthalene dicarboxylate), porph?a MOM-5, are cyclic macrocycle); each porphi(a)MOM is capable of variable particularly noteworthy. All three MOMs are anionic and loading of the encapsulated porphyrin (or other heterocyclic cationic metalloporphyrins are 100% loaded into cavities that are templated by MTMPyP cations. Porph(a)MOM-1 crystal macrocycle) in order to fine tune the porosity and catalytic lizes in the trigonal space group P-3 with a-b=30.4643(6) A activity; catalyst recycling can be accomplished in a facile and c=10.0841(4) A; V=8104.9(4) A3. It exhibits a novel manner via filtration. honeycomb-like 3D structure built from 3-connected Cd 0.161 Having described the invention in detail, it will be (COO)—and 5-connected CdCCOO)s— nodes (FIG. 2). apparent that modifications and variations are possible with Notably, the porphyrin moieties coordinate to CdCII) cations out departing the scope of the invention defined in the and are located in one set of channels (the nearest distance to appended claims. Furthermore, it should be appreciated that adjacent metalloporphyrins is ca. 1 nm) and every metal all examples in the present disclosure are provided as non loporphyrin is exposed to a second set of channels that rep limiting examples. resent 39.3% of the volume of the unit cell (PLATON was 0162 The following non-limiting examples are provided used to measure free volume for all structures described to further illustrate the present invention. It should be appre herein). The solvent channels and the lability of the Cd cat ciated by those of skill in the art that the techniques disclosed ions facilitated metal ion exchange by soaking crystals of in the examples that follow represent approaches the inven Cd-porphi(a)MOM-1 for four days in a MeOH solution of tors have found function well in the practice of the invention, MnCl as verified by disappearance of the UV Soret band of and thus can be considered to constitute examples of modes CdTMPyPat ~430 nm and appearance of strong Soret bands for its practice. However, those of skill in the art should, in for Mn(III)TMPyPat ~460 nm (see supplementary informa light of the present disclosure, appreciate that many changes tion). Mn-porphi(a)MOM-1 catalyses styrene oxidation: after can be made in the specific embodiments that are disclosed 10 hrs 61% conversion was observed (TOF=404 h-1), com and still obtain a like or similar result without departing from pared to conversion of only ~5% for an equivalent amount of the spirit and scope of the invention. US 2013/018445.6 A1 Jul. 18, 2013 22

Example 1 Templated Synthesis of POR(a)MOM-1 0163 A. Reaction with Porphyrin as Template

CdCl2 3.0 mL DMF por(a)MOM-1 0.5 mL HO Cd,(BTC) 850 C. 1.5CdTMPyP(HO). 2Cl -> Crystal system = Trigonal Space group = P-3 (2) () a = b = 30.5069(8) A; c = 10.1233(5) A: C = B = 90°: y = 120°; V = 8159(19) A

(2) (3)

TMPyP

HOOC COOH

COOH

(3) indicates text missing or illegible when filed

0164 B. Reaction without Porphyrin diffraction (a Bruker D8 Advance X-ray diffractometer at 20 kV, 5 mA for Cu (-1.5418 A). When this reaction was conducted under the same conditions but in the absence of CdCl TMPyP, tiny needle-like colorless crystals of different PXRD 2 pattern to por(a)MOM-1 were obtained. HOOC COOH 3.08 mLML DMF 5 colicyNeedle-lik als (0167. D. Crystal Structure of por(a)MOM-1 sc. ENS" 0168 Data were collected for a single crystal of different PXRD por(a)MOM-1 on a Bruker-AXS SMART APEX/CCD dif pattern to that fractometer using Cu, radiation (-1.5418 A.T=100(2)K). COOH of por(a)MOM-1obtained. were Data integration and reduction were performed using Saint BTC Plus 6.01. Absorption correction was performed by multi scan method implemented in SADABS. Space group was (0165 C. Procedure for Preparation of por(a)MOM-1 determined using XPREP implemented in APEX2. The crys (0166 CdCl4H2O (Fisher Scientific, 36.7 mg, 0.20 tal structure was solved using SHELXS-97, expanded using mmol), 1,3,5-benzenetricarboxylic acid (BTC) (Fisher Sci Fourier methods and refined on F using nonlinear least entific, 21.0 mg, 0.10 mmol) and meso-tetra(N-methyl-4- squares techniques with SHELXL-97 contained in APEX2 pyridyl) porphine tetratosylate (TMPyP) (Frontier Scientific, and WinGX v1.70.01 program packages. por(a)MOM-1 4.0 mg, 0.0044 mmol) were added to a 3.5 mL solution of adopts the trigonal space group P-3 and exhibits a honey DMF (3.0 mL) and HO (0.5 mL) in a 7.0 mL scintillation vial comb-like structure. There are two different cadmium build and heated at 85°C. for 12 hrs. The reaction mixture was ing blocks, Cd(COO), and CdCOO), which can be cooled to room temperature and dark prism crystals of simplified as 3- and 5-connected nodes to link the BTC por(a)MOM-1 were harvested and washed with methanol. ligands into a 3, 3, 3, 5-connected net. Porphyrin molecules Yield=5.5 mg (~7.0%, based on CdCl2). Crystals of are located in one type of channel whereas a second channel por(a)MOM-1 were characterized by FT-IR spectroscopy contains disordered guest molecules or ions. The distance (Nicolet Avatar 320 FTIR, diffuse reflectance, thermogravi between two adjacent porphyrin molecules is ca. 1 nm (FIG. metric analysis (Perkin Elmer STA 6000) and powder X-ray 2). US 2013/018445.6 A1 Jul. 18, 2013 23

Example 2 (Nicolet Avatar 320 FTIR, diffuse reflectance), thermogravi metric analysis (Perkin Elmer STA 6000) and powder X-ray Templated Synthesis of POR(a)MOM-2 diffraction (a Bruker D8 Advance X-ray diffractometer at 20 0169. A. Reaction with Porphyrin as Template kV, 5 mA for Cu (-1.5418 A)). When this reaction was

3.0 mL. por(a)MOM-2 DMA O.5 mL. Crystal system = Orthorhombic HO Space group = Cmmm 850 C. a = 19.623(8) A: b = 44.246(18) A (2) c = 14.550(7) A; V= 12633(9)A

TMPyP

HOOC COOH

COOH BTC

(2) indicates text missing or illegible when filed

(0170 B. Reaction without Porphyrin conducted under the same conditions but in the absence of TMPyP triangular colorless crystals of a compound with a different PXRD pattern to that of por(a)MOM-2 were obtained. Zn(NO3)2 3.0 mL DMA Triangular shaped 0.5 mL HO colorless crystals (0173 D. Crystal Structure of por(a)MOM-2 HOOC COOH 850 C. of a compound 0.174 Data was collected for a single crystal of -> that exhibits a por(a)MOM-2 placedon a Bruker-AXSSMARTAPEX/CCD different PXRD pattern to that of diffractometer using Cut, radiation (-1.5418 A, T=100(2) por(a)MOM-2 K). Structure was solved using Patterson methods, expanded were obtained. using Fourier methods and refined using nonlinear least COOH squares techniques on F. Indexing was performed using BTC APEX2. Data integration and reduction were performed using SaintPlus 6.01. Absorption correction was performed by multi-scan method implemented in SADABS. Space (0171 C. Procedure for Preparation of por(a)MOM-2 group was determined using XPREP implemented in (0172 Zn(NO)6HO (Fisher Scientific, 59.5 mg, 0.20 APEX2. The crystal structure was solved using SHELXS-97, mmol), 1,3,5-benzenetricarboxylic acid (BTC) (Fisher Sci expanded using Fourier methods and refined on F using entific, 21.0 mg, 0.10 mmol) and meso-tetra(N-methyl-4- nonlinear least-squares techniques with SHELXL-97 con pyridyl) porphine tetratosylate (TMPyP) (Frontier Scientific, tained in APEX2 and WinGX v1.70.01 programs packages. 3.0 mg, 0.0033 mmol) were added to a 3.5 mL solution of por(a)MOM-2 crystallizes in the orthorhombic space group DMA (3.0 mL) and H2O (0.5 mL) in a 7.0 mL scintillation Cmmm and exhibits a three-dimensional structure. As shown vial and heated at 85°C. for 48 hrs. The reaction mixture was in FIG. 3, there are two different zinc building blocks, Zn, cooled to room temperature and dark block crystals of (COO) and Zn (OH)(COO)(H2O), which link the por(a)MOM-2 were harvested and washed with methanol. BTC ligands into a net with a new topology, a 3, 3, 4, 4, Yield=22.0 mg (~62.0%, based on Zn(NO)). Crystals of 6-connected net. Metalloporphyrin molecules are located por(a)MOM-2 were characterized by FT-IR spectroscopy within cavities to balance the anionic framework. US 2013/018445.6 A1 Jul. 18, 2013 24

Example 3 por(a)MOM-3 were harvested and washed with methanol. Yield=9.3 mg (~16.2%, based on Zn(NO)). Crystals of Templated Synthesis of POR(a)MOM-3 por(a)MOM-3 were characterized by FT-IR spectroscopy (0175 A. Reaction with Porphyrin as Template (Nicolet Avatar 320 FTIR, diffuse reflectance), thermogravi

Zn(NO3) 3.0 mL DMF por(a)MOM-3 0.5 mL, H2O ZnO(1.4-NPD)ZnTMPyP N () 850 C. Crystal system = Orthorhombic

Nie- -> Space group = Cmca a = 17.6321(5) A: b = 18.7219(4) A c = 41.5804(1) A; V = 13726.0(6) A

TMPyP

COOH

COOH 1,4-NPD

(2) indicates text missing or illegible when filed

(0176 B. Reaction without Porphyrin metric analysis (Perkin Elmer STA 6000) and powder X-ray diffraction (a Bruker D8 Advance X-ray diffractometer at 20 kV, 5 mA for Cu (-1.5418 A)). When this reaction was conducted under the same conditions but in the absence of Zn(NO3) 3.0 mL DMF Clear Solution, no solid. 0.5 mL HO TMPyP no solids were formed. COOH 85°C. (0179 D. Crystal Structure of por(a)MOM-3 0180 Data was collected for a single crystal of por(a)MOM-3 placedon a Bruker-AXSSMARTAPEX/CCD diffractometer using Cut radiation (-1.5418 A, T=100(2) K). Indexing was performed using APEX2. Data integration and reduction were performed using SaintPlus 6.01. Absorp COOH tion correction was performed by multi-scan method imple mented in SADABS. Space group was determined using 14-NPD XPREP implemented in APEX2. The crystal structure was solved using SHELXS-97, expanded using Fourier methods (0177) C. Procedure for Preparation of por(a)MOM-3 and refined on F using nonlinear least-squares techniques (0178 Zn(NO)6HO (Fisher Scientific, 59.5 mg, 0.20 with SHELXL-97 contained in APEX2 and WinGX v1.70.01 mmol), 1,4-naphthalene dicarboxylate (1,4-NPD) (Fisher program packages. por(a)MOM-3 adopts the orthorhombic Scientific, 21.6 mg, 0.10 mmol) and meso-tetra(N-methyl-4- space group Cmca and exhibits a 3D structure that is based pyridyl) porphine tetratosylate (TMPyP) (Frontier Scientific, upon a novel building block, ZnO(HO)(COO), (FIG. 4). 3.0 mg, 0.0033 mmol) were added to a 3.5 mL solution of This building block serves as a 7-connected node to link the DMF (3.0 mL) and HO (0.5 mL) in a 7.0 mL scintillation vial 1,4-NPD ligands into a SEV net. Metalloporphyrin mol and heated at 85°C. for 48 hrs. The reaction mixture was ecules are located the cavities to balance the anionic frame cooled to room temperature and dark block crystals of work. US 2013/018445.6 A1 Jul. 18, 2013 25

Example 4 0183 C. Procedure for Preparation of por(a)MOM-4 (0.184 Zn(NO)6HO (Fisher Scientific, 59.5 mg, 0.20 Templated Synthesis of POR(a)MOM-4 mmol), 4,4'-biphenyldicarboxylic acid (BPDA) (Fisher Sci 0181 A. Reaction with Porphyrin as Template entific, 24.2 mg, 0.10 mmol) and meso-tetra(N-methyl-4-

Zn(NO3)2 3.0 mL DMF por(a)MOM-4

0.5 mL, H2O ZnO(BPDA), ZnTMPyP 850 C. Crystal system = Monoclinic -> Space group = P2/c a = 17.245(5) A: b = 17.025(5) A; c = 43.661 (12) A: C = y = 90°; B = 95.214(5); V = 13726.0(6)

COOH BPDA

(2) indicates text missing or illegible when filed

0182 B. Reaction without Porphyrin pyridyl) porphine tetratosylate (TMPyP) (Frontier Scientific, 3.0 mg, 0.0033 mmol) were added to a 3.5 mL solution of DMF (3.0 mL) and HO(0.5 mL) in a 7.0 mL scintillation vial and heated at 85°C. for 48 hrs. The reaction mixture was cooled to room temperature and dark prism crystals of Zn(NO3)2 3.0 mL DMF Colorless prismatic crystals of 0.5 mL HO compound that exhibits a por(a)MOM-4 were harvested and washed with methanol. COOH 850 C. different powder X-ray Yield=7.4 mg (-8.8%, based on Zn(NO)). Crystals of -> diffraction pattern to that of por(a)MOM-4 were characterized by FT-IR spectroscopy por(a)MOM-4 (Nicolet Avatar 320 FTIR, diffuse reflectance), thermogravi metric analysis (Perkin Elmer STA 6000) and powder X-ray diffraction (a Bruker D8 Advance X-ray diffractometer at 20 kV, 5 mA for Cu (=1.5418 A). When this reaction was conducted under the same conditions but in the absence of TMPyP. colorless prismatic crystals of compound that exhib its a different PXRD pattern to that of por(a)MOM-4 were obtained. 0185. D. Crystal Structure of por(a)MOM-4 0186 Data was collected for a single crystal of COOH por(a)MOM-4 placedon a Bruker-AXSSMARTAPEX/CCD BPDA diffractometer using Cut, radiation (-1.5418 A, T=100(2) K). Indexing was performed using APEX2. Data integration and reduction were performed using SaintPlus 6.01. Absorp US 2013/018445.6 A1 Jul. 18, 2013 26 tion correction was performed by multi-scan method imple 0188 B. Reaction without Porphyrin mented in SADABS. Space group was determined using XPREP implemented in APEX2. The crystal structure was solved using SHELXS-97, expanded using Fourier methods Zn(NO3)2 3.0 mL DEF Block colorless crystals of a and refined on F using nonlinear least-squares techniques 0.5 mL HO compound that exhibits a different with SHELXL-97 contained in APEX2 and WinGX v1.70.01 COOH 850 C. PXRD pattern to that of program packages. por(a)MOM-4 adopts the monoclinic -> por(a)MOM-5 were obtained. space group P2/c and exhibits an interpenetrated structure (FIG. 5). There are two different zinc building blocks, Zn, (O)(COO), and Zn (O)(COO)s, which can be simpli fied as 6- and 5-connected nodes that connect BPDA ligands into a two-dimensional 5,6-connected net. por(a)MOM-4 exhibits 2D to 3D parallel type of interpenetration. Metal COOH loporphyrin molecules are located within cavities in the crys 1,4-NPD tallattice to balance the anionic framework. (0189 C. Procedure for Preparation of por(a)MOM-5 Example 5 (0190. Zn(NO), .6HO (Fisher Scientific, 59.5 mg, 0.20 mmol), 1,4-naphthalene dicarboxylate (1,4-NPD) (Fisher Templated Synthesis of POR(a)MOM-5 Scientific, 21.6 mg, 0.10 mmol) and meso-tetra(N-methyl-4- 0187 A. Reaction with Porphyrin as Template pyridyl) porphine tetratosylate (TMPyP) (Frontier Scientific,

Zn(NO3) 3.0 mL DEF por(a)MOM-5

0.5 mL HO Zn(14-NPD)ZnTMPyP 85° C. Crystal system = Orthorhombic -> Space group = Cmcm a = 20.525 (15) A: b = 21.985(17) A c = 36.040(13) A; V = 16263(22) A

TMPyP

COOH

COOH 1,4-NPD

(3) indicates text missing or illegible when filed US 2013/018445.6 A1 Jul. 18, 2013 27

3.0 mg, 0.0033 mmol) were added to a 3.5 mL solution of Metalloporphyrin molecules are located within the cavities of DEF (3.0 mL) and H2O (0.5 mL) in a 7.0 mL scintillation vial pcu network. and heated at 85°C. for 48 hrs. The reaction mixture was cooled to room temperature and dark prismatic crystals of Example 6 por(a)MOM-5 were harvested and washed with methanol. Yield=2.8 mg (~4.0%, based on Zn(NO)). Crystals of Templated Synthesis and Catalytic Activity of por(a)MOM-5 were characterized by FT-IR spectroscopy CoTMPyP(a)HKUST-1-Co, POR(aMOM-6 (Nicolet Avatar 320 FTIR, diffuse reflectance), thermogravi metric analysis (Perkin Elmer STA 6000) and powder X-ray 0193 A. Reaction with Porphyrin as Template

CoCl2 3.0 mL CoTMPyP(a)HKUST-1-Co

DMF Co2(BTC)(S)2xCoTMPyPCl 0.5 mL (S = HO or DMF, x = 0.05-1.00 H2O 85°C. depending upon the relative -> amount of porphyrin used during synthesis) Crystal system = Cubic Space group = Fm-3m a = 26.4292(11) A, V = 18460.9(13) A This compound is isostructural with HKUST-1-Cu which was previously reported by Williams et al.: Chui, S. S.Y.: Lo, S. M. F. : Charmant, J. P. H.; Orpen, A. G.; Williams, I. D. Science 1999, 283, 1148.

TMPyP

HOOC COOH

COOH BTC

(2) indicates text missing or illegible when filed diffraction (a Bruker D8 Advance X-ray diffractometer at 20 (0194 B. Reaction without Porphyrin kV, 5 mA for Cu (-1.5418 A)). When this reaction was conducted under the same conditions but in the absence of TMPyP block-shaped colorless crystals that exhibit a differ CoCl2 3.0 mL (Co(HCOO)(BTC)2(DMF). ent PXRD pattern to that of Por(a)MOM-5 were observed. DMF Crystal system = Trigonal 0.5 mL Space group = P-3 (0191). D. Crystal Structure of por(a)MOM-5 HO a = 13.975(2) A 85° C. c = 8.165(1) A, 0.192 Data was collected for a single crystal of -> V = 1380.990 A por(a)MOM-5 placedon a Bruker-AXSSMARTAPEX/CCD HOOC COOH This product was previously diffractometer using Cut radiation (-1.5418 A, T=100(2) reported by Xu et al.: He, J.; K). Indexing was performed using APEX2. Data integration Zhang, Y.; Pan, Q.: Yu, J.; Ding, H.; Xu, R. Microporous and reduction were performed using SaintPlus 6.01. Absorp Mesoporous Mater. 2006,90, tion correction was performed by multi-scan method imple 145. mented in SADABS. Space group was determined using COOH XPREP implemented in APEX2. The crystal structure was BTC solved using SHELXS-97, expanded using Fourier methods and refined on F using nonlinear least-squares techniques (0195 C. Procedure for Preparation and Catalytic Activity with SHELXL-97 contained in APEX2 and WinGX v1.70.01 of CoTMPyP(a)HKUST-1-Co program packages. por(a)MOM-5 adopts the orthorhombic 0196. In a typical reaction CoCl2.4H2O (Fisher Scientific, space group Cmcm and exhibits a 3D structure that is based 47.6 mg, 0.20 mmol), 1,3,5-benzenetricarboxylic acid (BTC) upon Zn4(COO)s clusters (FIG. 6). This cluster serves as (Fisher Scientific, 1.0 mg, 0.10 mmol) and meso-tetra(N- a 6-connected node to link the 14-NPD ligands into apcu net. methyl-4-pyridyl) porphine tetratosylate (TMPyP) (Frontier US 2013/018445.6 A1 Jul. 18, 2013 28

Scientific, 1.4 mg., 0.0015 mmol) were added to a 3.5 mL (0198 D. Crystal Structure of CoTMPyP(a)HKUST-1-Co solution of DMF (3.0 mL) and HO (0.5 mL) in a 7.0 mL 0199 Data were collected for a single crystal of scintillation vial and heated at 85°C. for 12 hrs. The reaction CoTMPyP(a)HKUST-Co at the Advanced Photon Source on mixture was cooled to room temperature and dark cubic crys beamline 151D-C of ChemMatCARS Sector 15 (=0.40663 tals of CoTMPyP(a)HKUST-1-Co were harvested and A, T=100(2) K). The crystal structure was solved using washed with methanol. Yield=5.1 mg (~15%, based on SHELXS-97, expanded using Fourier methods and refined on CoCl). Crystals of CoTMPyP(a)HKUST-1 -Co were charac F using nonlinear least-squares techniques with SHELXL terized by FT-IR spectroscopy (Nicolet Avatar 320 FTIR, 97 contained in APEX2 and WinGX v1.70.01 program pack diffuse reflectance), thermogravimetric analysis (Perkin ages. CoTMPyP(a)HKUST-1 -Co adopts space group Fm-3m, Elmer STA 6000) and powder X-ray diffraction (a Bruker D8 Advance X-ray diffractometer at 20 kV, 5 mA for Cu, (v1. a=26.4295(11) A. It is isostructural with HKUST-1 and there 5418 A)). When this reaction was conducted under the same fore exhibits tho topology. The tbo structure can be inter conditions but in the absence of TMPyP crystals of Co preted from two viewpoints, the polyhedral approach or the (HCOO)(BTC) (DMF) were obtained. The identity of net approach. With the former approach, the entire framework Co(HCOO)(BTC) (DMF), was confirmed by single can be disassembled into three polyhedral cages of Stoichi crystal X-ray crystallography and powder X-ray diffraction. ometry 1:1:2 as follows: small rhombihexahedron cage; cub (0197) The catalytic activity of CoTMPyP(a)HKUST-1 -Co octahedral cage; tetrahedral cage (FIG. 7). The cuboctahedral with respect to styrene oxidation was studied as follows: cage is the only one of the three cages that is well-suited for crystals of CoTMPyP(a)HKUST-1-Co (10.0 mg) were encapsulation of tetrasubstituted porphyrin molecules since its O, symmetry matches the porphyrin's D, symmetry (as a immersed in acetonitrile for 24 hrs, filtered and placed in a subgroup) and the spherical cavity (diameter ~13 A) is a good solution of 1 mmol styrene, 2 mmol t-BuOOH, 40 uL 1.2- size fit for the porphyrin ring (diameter ~10 A) of TMPyP. In dichlorobenzene (internal standard) and 5.0 mL acetonitrile. addition, the structure can also be interpreted as consisting of The reaction mixture was heated at 60° C. for 10 hrs and dicobalt tetracarboxylate paddlewheels serving as pillars to monitored by GC-MS (HP-5MS 5% PHENYL METHYL SILOXANE, 30 mx0.25 mmx0.25 um; injector: 250° C.: link 2D square grid or kagomé nets into 3D networks with Method: hold 1 min at 50° C., then rise to 120° C. with 7° TMPyP molecules lying in the interlayer region in a sandwich C./min: Detector: 170° C.: Carrier gas: He (1.1 mL/min)): fashion. styrene 4.7 min; benzaldehyde=6.1 min; 1,2-dichloroben Example 7 Zene-7.5 min; styrene oxide-8.2 min; benzoic acid=11.8 min. A control reaction without any catalyst was conducted Templated Synthesis and Catalytic Activity of under the same conditions and revealed <7% conversion (vs. FETMPYP(a)HKUST-1-FE, POR(aMOM-7 92% in the presence of CoTMPyP(a)HKUST-1-Co). 0200 A. Reaction with Porphyrin as Template

FeCl 3.0 mL DMF FeTMPyP(a)HKUST-1-Fe

0.5 mL, H2O Fe2(BTC)(S)2ClxFeTMPyPCls 85°C. (S = HO or DMF, x = 0.05 -> 1.00 depending upon the relative amount of porphyrin used during synthesis) Crystal system = Cubic Space group = Fm-3m a = 26.5717(17) A, V = 18761(2) A This compound is isostructural with HKUST-1-Cu which was previously reported by Williams et al.: Chui, S. S.Y.: Lo, S. M. F.; Chairmant, J. P. H.; Orpen, A. G.; Williams, I. D. Science 1999, 283, 1148.

TMPyP US 2013/018445.6 A1 Jul. 18, 2013 29

-continued

HOOC COOH

COOH BTC (2) indicates text missing or illegible when filed

0201 B. Reaction without Porphyrin C./min: Detector: 170° C.: Carrier gas: He (1.1 mL/min)): styrene=4.7 min; benzaldehyde=6.1 min; 1,2-dichloroben Zene-7.5 min; styrene oxide-8.2 min; benzoic acid=11.8 FeCl 3.0 mL Yellow precipitate of a min. After the catalytic reaction was concluded the reaction DMF compound that exhibits a solution was filtered and the filtrant was recycled to evaluate HOOC COOH 0.5 mL different powder X-ray H2O diffraction pattern to that of whether or not it had retained its catalytic activity. Even after 85° C. FeTMPyP(a)HKUST-1-Fe seven 10hr cycles >55% conversion of styrene was observed. Two control reactions were conducted for comparison pur poses: a homogeneous reaction with an equivalent molar COOH amount of commercially available FeTMPyP; a homogenous BTC reaction without any catalyst. When these control reactions were conducted using the same solvent system, temperature 0202 C. Procedure for Preparation of and duration <7% and ca. 35% conversion of styrene, respec FeTMPyP(a)HKUST-1-Fe tively, were observed. 0205 D. Crystal Structure of FeTMPyP(a)HKUST-1-Fe 0203. In a typical reaction FeC1.4H2O (Fisher Scientific, 0206 Data were collected for a single crystal of 39.8 mg, 0.20 mmol), 1,3,5-benzenetricarboxylic acid (BTC) FeTMPyP(a)HKUST-Fe placed on a Bruker-AXS SMART (Fisher Scientific, 21.0 mg, 0.10 mmol) and meso-tetra(N- APEX/CCD diffractometer using Cu, radiation (v1.5418 methyl-4-pyridyl) porphine tetratosylate (TMPyP) (Frontier A, T=100(2)K). Indexing was performed using APEX2. Data Scientific, 1.4 mg., 0.0015 mmol) were added to a 3.5 mL integration and reduction were performed using SaintPlus solution of DMF (3.0 mL) and HO (0.5 mL) in a 7.0 mL 6.01. Absorption correction was performed by multi-scan scintillation vial and heated at 85°C. for 12 hrs. The reaction method implemented in SADABS. Space group was deter mixture was cooled to room temperature and dark cubic crys mined using XPREP implemented in APEX2. The crystal tals of FeTMPyP(a)HKUST-1-Fe were harvested and washed structure was solved using SHELXS-97, expanded using with methanol. Yield=13.1 mg (-30.9% based on FeCl). Fourier methods and refined on F using nonlinear least Crystals of FeTMPyP(a)HKUST-1-Fe were characterized by squares techniques with SHELXL-97 contained in APEX2 FT-IR spectroscopy (Nicolet Avatar 320 FTIR, diffuse reflec and WinGX v1.70.01 program packages. tance), thermogravimetric analysis (PerkinElmer STA 6000) FeTMPyP(a)HKUST-1-Fe adopts space group Fm-3m, a 26. and powder X-ray diffraction (a Bruker D8 Advance X-ray 5717(17) A. It is isostructural with HKUST-1 and therefore diffractometer at 20kV.5 mA for Cu (=1.5418 A)). When exhibits tho topology. The tbo structure can be interpreted this reaction was conducted under the same conditions but in from two viewpoints, the polyhedral approach or the net the absence of TMPyP, a yellow precipitate of a compound approach. With the former approach, the entire framework that exhibits a different powder X-ray diffraction pattern to can be disassembled into three polyhedral cages of Stoichi that of FeTMPyP(a)HKUST-1-Fe was obtained. ometry 1:1:2: Small rhombihexahedron cage, cuboctahedral cage, and tetrahedral cage (FIG. 8). The cuboctahedral cage is 0204. The catalytic activity of FeTMPyP(a)HKUST-1-Fe the only one of the three cages that is well-suited for encap with respect to styrene oxidation was studied as follows: sulation of tetrasubstituted porphyrin molecules since its O, Crystals of FeTMPyP(a)HKUST-1-Fe (10.0 mg) were symmetry matches the porphyrin's D, symmetry (as a Sub immersed in acetonitrile for 24 hrs, filtered and placed in a group) and the spherical cavity (diameter ~13 A) is a good solution of 1 mmol styrene, 2 mmol t-BuOOH, 40 uL 1.2- size fit for the porphyrin ring (diameter ~10 A) of TMPyP. In dichlorobenzene (internal standard) and 5.0 mL acetonitrile. addition, the structure can also be interpreted as consisting of The reaction mixture was heated at 60° C. for 10 h and diron tetracarboxylate paddlewheels serving as pillars to link monitored by GC-MS (HP-5MS 5% PHENYL METHYL 2D square grid or kagomé nets into 3D networks with TMPyP SILOXANE, 30 mx0.25 mmx0.25 um; injector: 250° C.: molecules lying in the interlayer region in a sandwich fash Method: hold 1 min at 50° C., then rise to 120° C. with 7° 1O. US 2013/018445.6 A1 Jul. 18, 2013 30

Example 8 acterized by FT-IR spectroscopy (Nicolet Avatar 320 FTIR, diffuse reflectance, thermogravimetric analysis (Perkin Templated Synthesis and Catalytic Activity of Elmer STA 6000) and powder X-ray diffraction (a Bruker D8 Advance X-ray diffractometer at 20 kV, 5 mA for Cu, (v1. MNTMPYP(a)HKUST-1-MN, POR(aMOM-8 5418 A)). When this reaction was conducted under the same 0207 A. Reaction with Porphyrin as Template conditions but in the absence of TMPyP crystals of Mn

MnCl 3.0 mL DMF MnTMPyP(a)HKUST-1-Mn

850 C. (S = HO or DMF, x = 0.05-1.00 depending upon the relative amount of porphyrin used during synthesis) Crystal system = Cubic Space group = Fm-3m a = 26.597 (2) A, V = 18460.9(13) A This compound is isostructural with HKUST-1-Cu which was previously reported by Williams et al.: Chui, S. S.Y.: Lo, S. M. F.; Charmant, J. P. H.; Orpen, A. G.; Williams, I. D. Science 1999, 283, 1148.

TMPyP

HOOC COOH

COOH BTC

(2) indicates text missing or illegible when filed

0208 B. Reaction without Porphyrin (HCOO)(BTC) (DMF) were obtained. The identity of Mn(HCOO)(BTC) (DMF), was confirmed by both of single crystal X-ray crystallography and powder X-ray diffrac tion. The catalytic activity of MnTMPyP(a)HKUST-1-Mn MnCl 3.0 mL Mn(HCOO)(BTC) (DMF), DMF Crystal system = Trigonal with respect to styrene oxidation was studied as follows: HOOC COOH 0.5 L Space group = P-3 Crystals of MnTMPyP(a)HKUST-1-Mn (10.0 mg) were HO a = 13.90 A immersed in acetonitrile for 24 hrs, filtered and placed in a 85° C. c = 8.11 A, -> V = 1434.454. A solution of 1 mmol styrene, 2 mmol t-BuOOH, 40 uL 1.2- This product was previously dichlorobenzene (internal standard) and 5.0 mL acetonitrile. reported by Kitagawa et al.: The reaction mixture was heated at 60° C. for 10 hrs and COOH Chen, J.; Ohba, M.: Kitagawa, monitored by GC-MS (HP-5MS 5% PHENYL METHYL BTC S. Chem. Lett. 2006, 35,526. SILOXANE, 30 mx0.25 mmx0.25 um; injector: 250° C.: Method: hold 1 min at 50° C., then rise to 120° C. with 7° C./min: Detector: 170° C.: Carrier gas: He (1.1 mL/min)): 0209 C. Procedure for Preparation of styrene=4.7 min; benzaldehyde=6.1 min; 1,2-dichloroben MnTMPyP(a)HKUST-1-Mn Zene-7.5 min; styrene oxide-8.2 min; benzoic acid=11.8 0210. In a typical reaction MnCl2.4H2O (Fisher Scientific, min. A control reaction was conducted for comparison pur 38.4 mg., 0.20 mmol), 1,3,5-benzenetricarboxylic acid (BTC) poses: a homogeneous reaction with an equivalent molar (Fisher Scientific, 21.0 mg, 0.10 mmol) and meso-tetra(N- amount of commercially available MnTMPyP was conducted methyl-4-pyridyl) porphine tetratosylate (TMPyP) (Frontier using the same solvent system, temperature and duration. Scientific, 1.4 mg., 0.0015 mmol) were added to a 3.5 mL <64% conversion of styrene was observed (vs. 81% for reac solution of DMF (3.0 mL) and HO (0.5 mL) in a 7.0 mL tion conducted in the presence of MnTMPyP(a)HKUST-1- scintillation vial and heated at 85°C. for 12 hrs. The reaction Mn). mixture was cooled to room temperature and dark cubic crys 0211 D. Crystal Structure of MnTMPyP(a)HKUST-1-Mn tals of MnTMPyP(a)HKUST-1-Mn were harvested and 0212 Data were collected for a single crystal of washed with methanol. Yield=2.5 mg (-6.0%, based on MnTMPyP(a)HKUST-1-Mn at the Advanced Photon Source MnCl). Crystals of MnTMPyP(a)HKUST-1-Mn were char on beamline 151D-C of ChemMatCARS Sector 15 (=0. US 2013/018445.6 A1 Jul. 18, 2013

40663 A, T=100(2)K). The crystal structure was solved using 0214 B. Reaction without porphyrin SHELXS-97, expanded using Fourier methods and refined on F using nonlinear least-squares techniques with SHELXL 97 contained in APEX2 and WinGX v1.70.01 program pack Ni(OAC) 2.0 mL Prismatic light green crystals ages. MnTMPyP(a)HKUST-1-Mn adopts space group DMF of a compound that exhibits a Fm-3m, a=26.597(2) A. It is isostructural with HKUST-1 and HOOC COOH 0.4 mL different powder X-ray therefore exhibits tho topology. The tbo structure can be H2O diffraction pattern to that of interpreted from two viewpoints, the polyhedral approach or 85° C. NiTMPyP(a)HKUST-2-Ni the net approach. With the former approach, the entire frame -> were obtained. work can be disassembled into three polyhedral cages of stoichiometry 1:1:2 as follows: small rhombihexahedron COOH cage; cuboctahedral cage; tetrahedral cage (FIG.9). The cub BTC octahedral cage is the only one of the three cages that is well-suited for encapsulation of tetrasubstituted porphyrin 0215 C. Procedure for Preparation of molecules since its O, Symmetry matches the porphyrin's D, NiTMPyP(a)HKUST-2-Ni symmetry (as a subgroup) and the spherical cavity (diameter 0216) In a typical reaction Ni(OAC).4H2O (Fisher Scien ~13 A) is a good size fit for the porphyrin ring (diameter ~10 tific, 8.3 mg, 0.03 mmol), 1,3,5-benzenetricarboxylic acid A) of TMPyP. In addition, the structure can also be interpreted (BTC) (Fisher Scientific, 10.5 mg, 0.05 mmol) and meso as consisting of dimanganese tetracarboxylate paddlewheels tetra(N-methyl-4-pyridyl) porphine tetratosylate (TMPyP) serving as pillars to link 2D square grid or kagomé nets into (Frontier Scientific, 2.0 mg, 0.0022 mmol) were added to a 3D networks with TMPyP molecules lying in the interlayer 2.4 mL solution of DMF (2.0 mL) and H2O (0.4 mL) in a 7.0 region in a sandwich fashion. mL scintillation vial and heated at 85° C. for 48 hrs. The reaction mixture was cooled to room temperature and red Example 9 cubic crystals of NiTMPyP(a)HKUST-2-Ni were harvested and washed with methanol. Yield=5.0 mg (-66%, based on Templated Synthesis of NiTMPyP(a)HKUST-2-Ni, Ni(OAC)). Crystals of NiTMPyP(a)HKUST-2-Ni were char acterized by FT-IR spectroscopy (Nicolet Avatar 320 FTIR, POR(aMOM-9 diffuse reflectance), thermogravimetric analysis (Perkin 0213 A. Reaction with Porphyrin as Template Elmer STA 6000) and powder X-ray diffraction (a Bruker D8

Ni(OAC) 2.0 mL DMF NiTMPyP(a)HKUST-2-Ni

0.4 mL H2O Nilo(BTC)(H2O)2(S)xNITMPyP 85°C. (S = HO or DMF, x = 0.05-1.00 -> depending upon the relative amount of porphyrin used during synthesis) Crystal system = Cubic Space group = Fm-3m a = 27.4849(8) A, V = 20747(3) A

TMPyP

HOOC COOH

COOH BTC

(3) indicates text missing or illegible when filed US 2013/018445.6 A1 Jul. 18, 2013 32

Advance X-ray diffractometer at 20 kV, 5 mA for Cu, (v1. Example 10 5418 A)). When this reaction was conducted under the same conditions but in the absence of TMPyP. prismatic light green Templated Synthesis of crystals were obtained of a compound that exhibits a different MGTMPYP(a)HKUST-2-MG, POR(aMOM-10 powder X-ray diffraction pattern to that of NiTMPyP(a)HKUST-2-Ni. 0219 A. Reaction with Porphyrin as Template

Mg(OAC). 2.0 mL. MgTMPyP(a)HKUST-2-Mg DMF Mgo (BTC)3(H2O)2(S)s XMgTMP 0.4 mL yP (S = HO or DMF, x = 0.05 HO 85°C. 1.00 depending upon the relative amount of porphyrin used during synthesis)

TMPyP

HOOC COOH

COOH BTC

(2) indicates text missing or illegible when filed

0217 D. Crystal Structure of NiTMPyP(a)HKUST-2-Ni 0220 B. Reaction without Porphyrin 0218 Data were collected for a single crystal of NiTMPyP(a)HKUST-2-Ni placed on a Bruker-AXS SMART APEX/CCD diffractometer using Cu, radiation (v1.5418 A, T=100(2)K). Indexing was performed using APEX2. Data Mg(OAC). integration and reduction were performed using SaintPlus HOOC COOH 2.0 ml DMF Prismatic colorless 6.01. Absorption correction was performed by multi-scan 0.4 ml H2O crystals of a method implemented in SADABS. Space group was deter 850 C. compound that mined using XPREP implemented in APEX2. The crystal -> exhibits a different structure was solved using SHELXS-97, expanded using powder X-ray diffraction pattern to Fourier methods and refined on F using nonlinear least COOH that of squares techniques with SHELXL-97 contained in APEX2 BTC MgTMPyP(a)HKUST and WinGX v1.70.01 program packages. 2-Mg NiTMPyP(a)HKUST-2-Ni adopts space group Fm-3m, a 27. were obtained. 4849(8) A. It has the same tho topology to HKUST-1. How ever, the building blocks in NiTMPyP(a)HKUST-2-Ni are Ni(HO)(COO), and Ni(HO)(COO). The tbo 0221 C. Procedure for Preparation of structure (FIG. 10) can be disassembled into three polyhedral MgTMPyP(a)HKUST-2-Mg cages of Stoichiometry 1:1:2: Small rhombihexahedron cage, 0222. In a typical reaction Mg(OAC).4H2O (Fisher Sci cuboctahedral cage, and tetrahedral cage. The cuboctahedral entific, 6.4 mg., 0.03 mmol), 1,3,5-benzenetricarboxylic acid cage is the only one of the three cages that is well-suited for (BTC) (Fisher Scientific, 10.5 mg, 0.05 mmol) and meso encapsulation of tetrasubstituted porphyrin molecules since tetra(N-methyl-4-pyridyl) porphine tetratosylate (TMPyP) its O, Symmetry matches the porphyrin's D, symmetry (as a (Frontier Scientific, 2.0 mg, 0.0022 mmol) were added to a Subgroup) and the spherical cavity is a good size fit for the 2.4 mL solution of DMF (2.0 mL) and H2O (0.4 mL) in a 7.0 porphyrin ring of TMPyP. mL scintillation vial and heated at 85° C. for 48 hrs. The US 2013/018445.6 A1 Jul. 18, 2013 33 reaction mixture was cooled to room temperature and dark 0226 B. Reaction without Porphyrin red cubic crystals of MgTMPyP(a)HKUST-2-Mg were har vested and washed with methanol. Yield=2.1 mg (-30.3%, based on Mg(OAC)). Crystals of MgTMPyP(a)HKUST-2- Mg were characterized by FT-IR spectroscopy (Nicolet Ava- CdCl2 tar 320 FTIR, diffuse reflectance), thermogravimetric analy- COOH 2.0 mL. Prism colorless sis (PerkinElmer STA 6000) and powder X-ray diffraction (a DMF crystals of a compound Bruker D8 Advance X-ray diffractometer at 20 kV, 5 mA for 0.5 LHO that exhibit a different Cu, (v-1 5418A)). When this reaction was conducted under sc. th),ENONE 11 the same conditions but in the absence of TMPyP. prismatic were obtained. colorless crystals were obtained of a compound that exhibits a different powder X-ray diffraction pattern to that of MgTMPyP(a)HKUST-2-Mg. 0223 D. Crystal Structure of MgTMPyP(a)HKUST-2-Mg 0224. The experimental PXRD pattern of MgTMPyP(a)HKUST-2-Mg matches the calculated PXRD HOOC COOH pattern of NiTMPyP(a)HKUST-2-Ni indicating that BPT MgTMPyP(a)HKUST-2-Mg is isostructural with NiTMPyP(a)HKUST-2-Ni. 0227 C. Procedure for Preparation of Por(a)MOM-11 0228. CdCl(Fisher Scientific, 91.7 mg, 0.50 mmol), Example 11 biphenyl-3,4,5-tricarboxylate (HBPT) (Fisher Scientific, Templated Synthesis of POR(a)MOM-11 14.8his mg, 0.05RyRS mmol) and meso-tetra(N-methyl-4-pyridyl RSsER. E. t 0225. A. Reaction with Porphyrin as Template 0.011 mmol) were added to DMF (2.0 mL) and HO (0.5 mL)

CdCl2

2.0 Por(a)MOM-11 mL Cd6 (BPT)Cl. (H2O). CH3NsCdCIHO solvent DMF Crystal system = Tetragonal O.5 mL. Space group = P4in HO a = b = 28.9318(4)A; c = 10.3646(3) A: 850 C. C = B = y = 90°; V = 8675.7(3)A

TMPyP

COOH

HOOC COOH BPT

() indicates text missing or illegible when filed US 2013/018445.6 A1 Jul. 18, 2013 34 in a 7.0 mL scintillation vial and heated at 85°C. for 12 hrs. Cd(II) cations, Cd1 and CdZ, one crystallographically inde The reaction mixture was cooled to room temperature and pendent BPT ligand and one crystallographically ordered dark-red prism crystals of Por(a)MOM-11 were harvestedand CdTMPyP cation. Cd2 adopts a distorted octahedral geom washed with methanol. Crystals of Por(a)MOM-11 were etry via coordination to four carboxylate oxygen atoms, an characterized by thermogravimetric analysis (Perkin Elmer aqua ligand and al-chloride anion. Cd1 possesses distorted STA 6000) and powder X-ray diffraction (a Bruker D8 octahedral geometry through four carboxylate oxygen atoms Advance X-ray diffractometer at 20 kV, 5 mA for Cu (v1. and two L-chloride anions. Cd-O bond distances range 5418 A)). When this reaction was conducted under the same from 2.205(5) to 2.392(5) A and Cd–Cl bond distances lie conditions but in the absence of TMPyP. prism colorless between 2.560(2) and 2.682(7) A, both ranges being consis crystals of different PXRD pattern to Por(a)MOM-11 were tent with expected values. Cd1 and Cd2 thereby form a 6-con obtained. nected trimetallic molecular building block (MBB), Cd(Cl) 0229. D. Crystal Structure of Por(a)MOM-11 (COO)’. These MBBs are linked by 3-connected BPT 0230 Data were collected for a single crystal of ligands to form a 3.6-connected network with Schläfli symbol Por(a)MOM-11 on a Bruker-AXS SMART APEX/CCD dif {4,6}{4°06'0.8}. Projecting the structure along the c fractometer using Cu, radiation (-1.5418 A.T=100(2)K). axis (FIG. 11) reveals that there is a 1:1 ratio of two types of Data integration and reduction were performed using Saint square channel: (A) ~12.6 Ax12.6 A.; (B) ~11.9 Ax11.9 A Plus 6.01. Absorption correction was performed by multi (after subtracting van der Waals radii). CdTMPyP cations scan method implemented in SADABS. Space group was stack in channel A separated by 10.3 A whereas channel B is determined using XPREP implemented in APEX2. The crys occupied by solvent molecules. tal structure was solved using SHELXS-97, expanded using Fourier methods and refined on F using nonlinear least Example 12 squares techniques with SHELXL-97 contained in APEX2 and WinGX v1.70.01 program packages. FIG. 11 reveals that Templated Synthesis of POR(a)MOM-12 the framework of Por(a)MOM-11 contains two independent 0231 A. Reaction with Porphyrin as Template

Cd(NO)

2.0 Por(a)MOM-12 mL Cod (BPT), CHNCd(solvent) solventCrystal DMF system = Triclinic 0.4 mL Space group = P-1 HO a = 10.027(3) A: 850 C. b = 18.420(5)A: -> c = 20.577(6)A: C = 89.269(7): B = 84.18O(7): Y = 88.402(6): V = 3779.3(19)A

TMPyP

COOH

HOOC COOH BPT

(2) indicates text missing or illegible when filed US 2013/018445.6 A1 Jul. 18, 2013 35

0232 B. Reaction without Porphyrin 0235. D. Crystal Structure of Por(a)MOM-12 0236 Crystallographic data were collected on a single crystal of Por(a)MOM-12 using a Bruker-AXS SMART CdCNO), APEX/CCD diffractometer and Cu, radiation (-1.5418 A. T=100(2) K). Data integration and reduction were performed COOH 2.0 mL. Prism colorless DMF crystals of a compound using SaintPlus 6.01. Absorption correction was performed 0.4 mL H2O that exhibit a different by multi-scan method implemented in SADABS. Space 85°C. PXRD pattern to group was determined using XPREP implemented in -> that of Por(a)MOM-12 were obtained. APEX2. The crystal structure was solved using SHELXS-97, expanded using Fourier methods and refined on F using nonlinear least-squares techniques with SHELXL-97 con tained in APEX2 and WinGX v1.70.01 program packages. Single crystal x-ray diffraction (SCXRD) reveals that por(a)MOM-12 is an anionic framework encapsulating cat HOOC COOH ionic porphyrins in alternatingchannels (FIG. 12). FIG. 12 BPT illustrates how the framework of por(a)MOM-12 contains two crystallographically independent Cd atoms (Cd1 and Cd2). 0233 C. Procedure for Preparation of Por(a)MOM-12 Cd1 exhibits pentagonal bipyramidal geometry via coordina 0234 Cd(NO), .4H2O (Fisher Scientific, 15.4 mg., 0.05 mmol), biphenyl-3,4,5-tricarboxylate (HBPT) (Fisher Sci tion to five carboxylate moieties, two of which are bidentate. entific, 14.8 mg, 0.05 mmol) and meso-tetra(N-methyl-4- Cd2 adopts distorted octahedral coordination geometry pyridyl) porphine tetratosylate (TMPyP) (Frontier Scientific, through six carboxylate oxygen atoms from five carboxylate 15.0 mg, 0.011 mmol) were added to DMF (2.0 mL) and HO moieties, one of which is bidentate. Cd—O bond distances (0.4 mL) in a 7.0 mL scintillation vial and heated at 85°C. for range from 2.241(4) A to 2.598(4) A, which is consistent with 12 hrs. The reaction mixture was cooled to room temperature expected values. Both Cd1 and Cd2 exist as dimers that in and dark prism crystals of Por(a)MOM-12 were harvestedand effect serve as 6-connected molecular building blocks washed with methanol. Crystals of Por(a)MOM-12 were (MBBs), Cd(COO)’. These MBBS serve as 6-connected characterized by thermogravimetric analysis (Perkin Elmer nodes that are linked by 3-connected BPT ligands to afford STA 6000) and powder X-ray diffraction (a Bruker D8 a (3.6)-connected rtl topology net. Advance X-ray diffractometer at 20 kV, 5 mA for Cu (v1. 5418 A)). When this reaction was conducted under the same Example 13 conditions but in the absence of TMPyP. prism colorless crystals of different PXRD pattern to Por(a)MOM-12 were Templated Synthesis of POR(a)MOM-13 obtained. 0237 A. Reaction with Porphyrin as Template

Cd(NO),

2.0 Por(a)MOM-13 mL Cd4(TPT). CH3NsCd solvent DMF Crystal system = Monoclinic 0.4 Space group = P21/c mL a = 14.050(2)A: HO b = 20.156(3)A: 850 C. c = 20.378(3)A: -> C = y = 90.00°: B = 101.717(6): V = 5650.6(14)A

TMPyP US 2013/018445.6 A1 Jul. 18, 2013 36

-continued Cd(NO), COOH

HOOC COOH HTPT

(2) indicates text missing or illegible when filed

0238 B. Reaction without Porphyrin

CdCNO),

COOH 2.0 mL. Prism colorless crystals of a DMF compound that exhibits a 0.4 mL different PXRD pattern to that HO of Por(a)MOM-13 were 850 C. obtained.

HOOC COOH HTPT

0239 C. Procedure for Preparation of Por(a)MOM-13 fractometer using Cut, radiation (-1.5418 A.T=100(2)K). 0240 Cd(NO), .4H2O (Fisher Scientific, 15.4 mg., 0.05 Data integration and reduction were performed using Saint mmol), 1,1':3", 1"-Terphenyl]-4.4".5"-tricarboxylate Plus 6.01. Absorption correction was performed by multi (HTPT) (Fisher Scientific, 20.0 mg, 0.05 mmol) and meso scan method implemented in SADABS. Space group was tetra(N-methyl-4-pyridyl) porphine tetratosylate (TMPyP) determined using XPREP implemented in APEX2. The crys (Frontier Scientific, 15.0 mg, 0.011 mmol) were added to tal structure was solved using SHELXS-97, expanded using DMF(2.0 mL) and HO (0.4 mL) in a 7.0 mL scintillation vial and heated at 85°C. for 12 hrs. The reaction mixture was Fourier methods and refined on F using nonlinear least cooled to room temperature and dark prism crystals of squares techniques with SHELXL-97 contained in APEX2 Por(a)MOM-13 were harvested and washed with methanol. and WinGX v1.70.01 program packages. Single crystal X-ray Crystals of Por(a)MOM-13 were characterized by thermo diffraction (SCXRD) reveals that por(a)MOM-13 is an gravimetric analysis (Perkin Elmer STA 6000) and powder anionic framework encapsulating cationic porphyrins in all X-ray diffraction (a Bruker D8 Advance X-ray diffractometer channels (FIG. 13). Por(a)MOM-13 contains one crystallo at 20 kV, 5 mA for Cup (-1.5418 A)). When this reaction graphically independent Cd atom which exhibits pentagonal was conducted under the same conditions but in the absence bipyramidal geometry via coordination to five carboxylate of TMPyP. prism colorless crystals of different PXRD pattern moieties, two of which are bidentate. Each Cd exists as to Por(a)MOM-13 were obtained. dimers that in effect serve as 6-connected molecular building 0241. D. Crystal Structure of Por(a)MOM-13 blocks (MBBs), Cd(COO)’. These MBBS serve as 6-con 0242 X-ray data were collected for a single crystal of nected nodes that are linked by 3-connected TPT ligands to Por(a)MOM-13 on a Bruker-AXS SMART APEX/CCD dif afforda (3.6)-connected rtl topology net. US 2013/018445.6 A1 Jul. 18, 2013 37

Example 14 Templated Synthesis of POR(a)MOM-14 0243 A. Reaction with Porphyrin as Template

2.0 Por(a)MOM-14 mL Zn (BPT) (COO). CH3NZn solventCrystal system = Triclinic 0.4 mL Space group = P-1 HO a = 10.1841 (12)A: 850 C. b = 20.701 (3)A: c = 20.951 (3)A: C = 88.105(3): B = 76.861(3): Y = 81.722(3): V = 4256.5(10)A

TMPyP

COOH

HOOC COOH BPT

(2) indicates text missing or illegible when filed

0244 B. Procedure for Preparation of Por(a)MOM-14 151D-C of ChemMatCARS Sector 15(-0.40663 A, T=100 0245 Zn(NO)6HO(Fisher Scientific, 29.7 mg, 0.10 (2) K). The crystal structure was solved using SHELXS-97, mmol), biphenyl-3,4,5-tricarboxylate (HBPT) (Fisher Sci expanded using Fourier methods and refined on F using entific, 14.8 mg, 0.05 mmol) and meso-tetra(N-methyl-4- nonlinear least-squares techniques with SHELXL-97 con pyridyl) porphine tetratosylate (TMPyP) (Frontier Scientific, tained in APEX2 and WinGX v1.70.01 program packages. 10.0 mg, 0.0073 mmol) were added to DMF (2.0 mL) and The framework of Por(a)MOM-14 contains two independent H2O (0.4 mL) in a 7.0 mL scintillation vial and heated at 85° Zn(II) cations which form a 6-connected trimetallic molecu C. for 24 hrs. The reaction mixture was cooled to room lar building block (MBB), Zn(COO), . These MBBs are temperature and dark-red needle-like crystals of Por(a)MOM linked by 3-connected BPT ligands to form a 3.6-connected 14 were harvested and washed with methanol. rtl network. Projecting the structure along thea axis (FIG. 14) 0246 C. Crystal Structure of Por(a)MOM-14 reveals that there is a 1:1 ratio of two types of square channels, 0247 Data were collected for a single crystal of which are occupied by solvent molecules and ZnTMPyP Por(a)MOM-14 at the Advanced Photon Source on beamline cations respectively. US 2013/018445.6 A1 Jul. 18, 2013

Example 15 Templated Synthesis of Por(a)MOM-15 0248 A. Reaction with Porphyrin as Template

ZnCl2

2.0 Por(a)MOM-15 mL Zn (BPT) (COO). CH3NZn solventCrystal DMA system = Triclinic Space group = P-1 a = 9.288(3)A: b = 27.370(8)A: c = 28.665 (8)A: C = 86.759(6): B = 81.697 (6): Y = 84.624(6): V = 7172(4)A

TMPyP

COOH

HOOC COOH BPT

(2) indicates text missing or illegible when filed

0249 B. Procedure for Preparation of Por(a)MOM-15 151D-C of ChemMatCARS Sector 15(-0.40663 A, T=100 (0250 ZnCl(Fisher Scientific, 29.7 mg, 0.10 mmol), (2) K). The crystal structure was solved using SHELXS-97, biphenyl-3,4,5-tricarboxylate (HBPT) (Fisher Scientific, expanded using Fourier methods and refined on F using 14.8 mg, 0.05 mmol) and meso-tetra(N-methyl-4-pyridyl) nonlinear least-squares techniques with SHELXL-97 con porphine tetratosylate (TMPyP) (Frontier Scientific, 10.0 mg. tained in APEX2 and WinGX v1.70.01 program packages. 0.0073 mmol) were added to DMA (2.0 mL) and HO (0.4 The framework of Por(a)MOM-15 contains two molecular mL) in a 7.0 mL scintillation vial and heated at 85°C. for 24 building blocks: five-connected Zn (OH)(COO), and hrs. The reaction mixture was cooled to room temperature six-connected Zn(COO). These MBBs are linked by and dark-red prism crystals of Por(a)MOM-15 were harvested 3-connected BPT ligands to form a 3.5-connected network. and washed with methanol. Projecting the structure along thea axis (FIG. 15) reveals that 0251 C. Crystal Structure of Por(a)MOM-15 there is a 1:1 ratio of two types of square channels, which are 0252 Data were collected for a single crystal of occupied by solvent molecules and ZnTMPyP cations, Por(a)MOM-15 at the Advanced Photon Source on beamline respectively. US 2013/018445.6 A1 Jul. 18, 2013 39

Example 16 Templated synthesis of Por(a)MOM-16 0253 A. Reaction with Porphyrin as Template

ZnCl2

2.0 mL. DMF 0.4 mL NDC). CH3NZn solventCrystal HO system = Triclinic 850 C. Space group = P-1 a = 10.294(4)A; b = 19.495 (8)A: c = 20.640(8)A; C = 108.767(7): B = 96.323(9): Y = 95.328(10); V = 3862(3)A

TMPyP

COOH

COOH 2,6-NDC

(2) indicates text missing or illegible when filed

0254 B. Procedure for Preparation of Por(a)MOM-16 Data integration and reduction were performed using Saint 0255 ZnC1 (Fisher Scientific, 29.7 mg, 0.10 mmol), 2,6- Plus 6.01. Absorption correction was performed by multi naphthalene dicarboxylic acid (Fisher Scientific, 10.8 mg, scan method implemented in SADABS. Space group was 0.05 mmol) and meso-tetra(N-methyl-4-pyridyl) porphine determined using XPREP implemented in APEX2. The crys tetratosylate (TMPyP) (Frontier Scientific, 10.0 mg 0.0073 tal structure was solved using SHELXS-97, expanded using mmol) were added to DMF (2.0 mL) and H2O (0.4 mL) in a Fourier methods and refined on F using nonlinear least 7.0 mL scintillation vial and heated at 85°C. for 24 hrs. The squares techniques with SHELXL-97 contained in APEX2 reaction mixture was cooled to room temperature and dark and WinGX v1.70.01 program packages. The framework red prism crystals of Por(a)MOM-16 were harvested and reveals that Por(a)MOM-16 is based upon six-connected washed with methanol. molecular building blocks of formula Zn3(COO). These MBBs are linked by 2-connected 2,6-NDC ligands to form a 0256 C. Crystal Structure of Por(a)MOM-16 6-connected pcu network. Projecting the structure along the a 0257 Data were collected for a single crystal of axis (FIG. 16) reveals that there is a 1:1 ratio of two types of Por(a)MOM-16 on a Bruker-AXS SMART APEX/CCD dif square channel, which are occupied by solvent molecules and fractometer using Cut, radiation (-1.5418 A.T=100(2)K). ZnTMPyP cations, respectively. US 2013/018445.6 A1 Jul. 18, 2013 40

Example 17 Templated Synthesis of Por(a)MOM-17 0258 A. Reaction with Porphyrin as Template

CdCl2

2.0 Por(a)MOM-17 mL Cods (BPT)Cl. CH3NCdCl solvent DMF Crystal system = Monoclinic Space group = P21 a = 10.294(4)A; b = 21.763(6)A: c = 21.183 (6)A; C = 90.00: B = 96.273 (7): Y = 90.00°: V = 4730(2)A

TMPyP

COOH

HOOC COOH BPT

0259 B. Procedure for Preparation of Por(a)MOM-17 Data integration and reduction were performed using Saint 0260 CdCl(Fisher Scientific, 18.3 mg, 0.1 mmol), biphe Plus 6.01. Absorption correction was performed by multi nyl-3,4,5-tricarboxylate (HBPT) (Fisher Scientific, 14.8 scan method implemented in SADABS. Space group was mg, 0.05 mmol) and meso-tetra(N-methyl-4-pyridyl) por determined using XPREP implemented in APEX2. The crys phine tetratosylate (TMPyP) (Frontier Scientific, 15.0 mg. tal structure was solved using SHELXS-97, expanded using 0.011 mmol) were added to DMF (2.0 mL) and HO (0.4 mL) Fourier methods and refined on F using nonlinear least in a 7.0 mL scintillation vial and heated at 85°C. for 12 hrs. squares techniques with SHELXL-97 contained in APEX2 After filtering the solid from solution, the filtrate was heated and WinGX v1.70.01 program packages. The framework of at 85°C. for 24hrs. Prism dark-red crystals of Por(a)MOM-17 Por(a)MOM-17 is based upon six-connected building blocks were harvested and washed with methanol. of formula CdCl(COO). These MBBs are linked by 0261 C. Crystal Structure of Por(a)MOM-17 3-connected BPT ligands to form a 3.6-connected rtl net 0262 Data were collected for a single crystal of work. Projecting the structure along thea axis reveals that all Por(a)MOM-17 on a Bruker-AXS SMART APEX/CCD dif square channels are occupied by CdTMPyP cations (FIG. fractometer using Cut, radiation (-1.5418 A.T=100(2)K). 17). US 2013/018445.6 A1 Jul. 18, 2013 41

Example 18 Templated Synthesis of Por(a)MOM-18 0263. A. Reaction with Porphyrin as Template

CoCl2

2.0 mL. Por(a)MOM-18 DMF Co4(BPT) (solvent). CHNsCo. solvent O.5 mL. Crystal system = Monoclinic HO Space group = C2/c 850 C. a = 30.984(11)A: b = 20.524(7)A: c = 18.948(7)A: C = 90.00: B = 101.818 (10); Y = 90.00°: V = 11794(7)A

TMPyP

COOH

HOOC COOH BPT

(2) indicates text missing or illegible when filed

0264 B. Procedure for Preparation of Por(a)MOM-18 Data integration and reduction were performed using Saint 0265 CoC1.6HO(Fisher Scientific, 23.7 mg, 0.10 Plus 6.01. Absorption correction was performed by multi mmol), biphenyl-3,4,5-tricarboxylate (HBPT) (Fisher Sci scan method implemented in SADABS. Space group was entific, 14.8 mg, 0.05 mmol) and meso-tetra(N-methyl-4- determined using XPREP implemented in APEX2. The crys pyridyl) porphine tetratosylate (TMPyP) (Frontier Scientific, tal structure was solved using SHELXS-97, expanded using 15.0 mg, 0.011 mmol) were added to a 2.5 mL solution of Fourier methods and refined on F using nonlinear least DMF (2.0 mL) and H2O (0.5 mL) in a 7.0 mL scintillation vial squares techniques with SHELXL-97 contained in APEX2 and heated at 85°C. for 24 hrs. Prism dark-red crystals of and WinGX v1.70.01 program packages. The framework of Por(a)MOM-18 were harvested and washed with methanol. Por(a)MOM-18 contains two molecular building blocks: two 0266 C. Crystal Structure of Por(a)MOM-18 connected Co(COO),(HO): six-connected Co(COO) 0267 Data were collected for a single crystal of (HO), . These MBBs are linked by BPT ligands to form a Por(a)MOM-18 on a Bruker-AXS SMART APEX/CCD dif 6-connected pts network. FIG. 18 illustrates how CoTMPyP fractometer using Cut, radiation (-1.5418 A.T=100(2)K). cations arrange in the channels along the b axis. US 2013/018445.6 A1 Jul. 18, 2013 42

Example 19 Templated Synthesis of Por(a)MOM-19 0268 A. Reaction with Porphyrin as Template

ZnCl2

2.0 mL. Por(a)MOM-19 DMF Zn4(BPT) (solvent). CH3NZn solvent 0.4 mL Crystal system = Tetragonal HO Space group = P4(2) incm 850 C. a = b = 22.4530(3)A: c = 42.0940(4)A: C = B = y = 90.00°:

TMPyP

COOH

HOOC COOH HTPT

(2) indicates text missing or illegible when filed

0269 B. Procedure for Preparation of Por(a)MOM-19 Data integration and reduction were performed using Saint (0270 ZnCl (Fisher Scientific, 29.7 mg, 0.10 mmol), 1,1': Plus 6.01. Absorption correction was performed by multi 3',1"-Terphenyl]-44",5'-tricarboxylate(HTPT) (Fisher Sci scan method implemented in SADABS. Space group was entific, 20.0 mg, 0.05 mmol) and meso-tetra(N-methyl-4- determined using XPREP implemented in APEX2. The crys pyridyl) porphine tetratosylate (TMPyP) (Frontier Scientific, tal structure was solved using SHELXS-97, expanded using 15.0 mg, 0.011 mmol) were added to DMF (2.0 mL) and HO (0.4 mL) in a 7.0 mL scintillation vial and heated at 85°C. for Fourier methods and refined on F using nonlinear least 24 hrs. The reaction mixture was cooled to room temperature squares techniques with SHELXL-97 contained in APEX2 and black prism crystals of Por(a)MOM-19 were harvested and WinGX v1.70.01 program packages. The framework of and washed with methanol. Por(a)MOM-19 contains two molecular building blocks: two (0271 C. Crystal Structure of Por(a)MOM-19 connected Zn(COO),(HO)," and six-connected Zn 0272 Data were collected for a single crystal of (COO). These MBBs are linked by TPT ligands to forma Por(a)MOM-19 on a Bruker-AXS SMART APEX/CCD dif 6-connected pts network. FIG. 19 illustrates how ZnTMPyP fractometer using Cut, radiation (-1.5418 A.T=100(2)K). cations arrange in the channels along the b axis. US 2013/018445.6 A1 Jul. 18, 2013 43

Example 20 Templated Synthesis of Por(a)MOM-20 0273 A. Reaction with Porphyrin as Template

CdCl2 2.0 mL. Por(a)MOM-20 DMF Cd(BTB), CHNCdCI). HO solvent 0.4 mL Crystal system = Tetragonal HO Space group = Pnca 850 C. a = b = 22.767 (6)A; c = 41.732(10)A: C = B = y = 90.00°: V = 4730(2)A

TMPyP

COOH

HOOC COOH HBTB

(2) indicates text missing or illegible when filed

(0274 B. Procedure for Preparation of Por(a)MOM-20 and WinGX v1.70.01 program packages. The framework of (0275 CdCl (Fisher Scientific, 36.6 mg, 0.20 mmol), Por(a)MOM-20 contains one four-connected molecular HBTB(Fisher Scientific, 23.3 mg, 0.05 mmol) and meso building block of formula CdCCOO). Projecting the tetra(N-methyl-4-pyridyl) porphine tetratosylate (TMPyP) structure along the b axis reveals that CdTMPyP cations are (Frontier Scientific, 10.0 mg, 0.0073 mmol) were added to located within the channels. DMF (2.0 mL) and H2O (0.4 mL) in a 7.0 mL scintillation vial and heated at 85°C. for 12 hrs. After filtering the solid from REFERENCES solution, the filtrate was heated at 85°C. for 24 hrs. Black 0278 1. Meunier, B. Metalloporphyrins as versatile cata crystals of Por(a)MOM-20 were harvested and washed with lysts for oxidation reactions and oxidative DNA cleavage. methanol. Chem. Rev. 92, 1411–1456 (1992). (0276 C. Crystal Structure of Por(a)MOM-20 0279 2. Batten, S. R., Neville, S. M. & Turner, D. R. 0277 Data were collected for a single crystal of Coordination Polymers: Design, Analysis and Application Por(a)MOM-20 on a Bruker-AXS SMART APEX/CCD dif (Royal Society of Chemistry, Cambridge, UK, 2009). fractometer using Cut, radiation (-1.5418 A.T=100(2)K). (0280 3. MacGillivary, L. R. Metal Organic Frameworks Data integration and reduction were performed using Saint (Wiley, 2010). Plus 6.01. Absorption correction was performed by multi 0281. 4. Furukawa, H. et al. Ultra-high porosity in metal scan method implemented in SADABS. Space group was organic frameworks, Science 239, 424-428 (2010). determined using XPREP implemented in APEX2. The crys 0282 5. Moulton, B. & Zaworotko, M.J. From molecules tal structure was solved using SHELXS-97, expanded using to crystal engineering: Supramolecular isomerism and Fourier methods and refined on F using nonlinear least polymorphism in network solids. Chem. Rev. 101, 1629 squares techniques with SHELXL-97 contained in APEX2 1658 (2001). US 2013/018445.6 A1 Jul. 18, 2013 44

0283 6. Kitagawa, S., Kitaura, R. & Noro, S. Functional 0301 24. Bajpe. S. R. et al. Direct observation of molecu porous coordination polymers. Angew. Chem. Int. Ed. 43. lar-level template action leading to self-assembly of a 2334-2375 (2004). porous framework. Chem. Eur. J. 16,3926-3932 (2010). 0284 7. Rosseinsky, M. J. Enlightened pores. Nature (0302) 25. Spek, A. L. Acta Cryst. A46, C34 (1990). Mater 9, 609-610 (2010). What is claimed is: 0285 8. Seo, J. S. et al. A homochiral metal-organic 1. A process for the preparation of a heterocyclic macro porous material for enantioselective separation and cataly cycle-templated Supramolecular metal organic material, the sis. Nature 404,982-986 (2000). process comprising preparing a mixture containing a metal, a 0286 9. Ono, K.Yoshizawa, M., Kato, T., Watanabe, K. & heterocyclic macrocycle, and organic ligands and forming, in Fujita, M. Porphine Dimeric Assemblies in Organic-Pil the mixture, a heterocyclic macrocycle-templated metal lared Coordination. Angew. Chem. 119, 1835-1838 organic material comprising the metal, the heterocyclic mac (2007). rocycle and the ligands by template-directed synthesis with (0287 10. Perry IV. J. J., Perman, J. A. & Zaworotko, M.J. the heterocyclic macrocycle serving as the template. Design and synthesis of metal-organic frameworks using 2. The process of claim 1 wherein the heterocyclic macro metal-organic polyhedra as molecular building blocks. cycle is a porphyrin, a porphyrazin, a chlorin, a corrin, or a Chem. Soc. Rev. 38, 1400-1417 (2009). porphyrinogen. 0288 11. Chui, S. S.-Y., Lo, S. M-F. Charmant, J. P. H., 3. The process of claim 1 wherein the heterocyclic macro Guy Orpen, A. & Williams, I. D. A chemically functional cycle is a metalated porphyrin, a metalated porphyrazin, a izable nanoporous material Cu(TMA).(H2O). Sci metalated chlorin, a metalated corrin, or a metalated porphy ence 283, 1148-1150 (1999). rinogen. 0289 12. Farha, O. F., Shultz, A. M., Sarjeant, A. A., 4. The process of claim 1 wherein the heterocyclic macro Nauyen, S.T. & Hupp, J.T. Active-site-accessible, porphy cycle is a metalated porphyrin, a metalated porphyrazin, a rinic metal-organic framework materials. J. Am. Chem. metalated chlorin, a metalated corrin, or a metalated porphy Soc. 133, 5652-5655 (2011). rinogen and the metal coordinated by the metalated porphy 0290 13. Larsen, R. W. et al. Metal-organic materials that rin, metalated porphyrazin, metalated chlorin, metalated cor selectively encapsulate metalloporphyrins, MOMZymes: rin, or metalated porphyrinogen is Sc, Ti, V. Cr, Mn, Fe, Co. A new paradigm for heme biomimetic catalysis. J. Am. Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, Chem. Soc. Accepted for publication May 2011. W. Re, Os, Ir, Pt, Au or Hg. 0291. 14. Alkordi, M. H. et al. Zeolite-like metal-organic 5. The process of claim 1 wherein the heterocyclic macro frameworks as platforms for applications: On metallopor cycle is a metalated porphyrin, a metalated porphyrazin, a phyrin-based catalysts. J. Am. Chem. Soc. 130, 12639 metalated chlorin, a metalated corrin, or a metalated porphy 12641 (2008). rinogen and the metal coordinated by the metalated porphy 0292 15. Lu, J. J., Mondal, A., Moulton, B. & Zaworotko, rin, metalated porphyrazin, metalated chlorin, metalated cor M. J. Polygons and faceted polyhedra and nanoporous rin, or metalated porphyrinogen is selected from Co. Cd, Mn, networks. Angew. Cheme. Int. Ed. 40, 21 13-2116 (2001). Zn, Fe, Ni, and combinations thereof. 0293 16. Xie, L. et al. Mixed-Valence Iron(II,III) Trime 6. The process of claim 1 wherein the organic ligand is sates with Open Frameworks Modulated by Solvents. linear, branched orcyclic and has the capacity to coordinate at Inorg. Chem. 46,7782-7788 (2007). least two metals. 0294 17. Maniam, P. & Stock, N. Investigation of porous 7. The process of claim 1 wherein the organic ligand is a Ni-based metal-organic frameworks containing paddle linker, containing two metal coordinating groups. wheel yype inorganic building units via high-throughput 8. The process of claim 1 wherein the organic ligand con methods. Inorg. Chem. DOI: 10.1021/ic200381 f(2011). tains at least 3 metal coordinating groups. 0295) 18. Sun, C.-Y. et al. Highly Stable Crystalline Cata 9. The process of claim 1 wherein the metal coordinating lysts Based on a Microporous Metal-Organic Framework groups are selected from among carboxylates, nitrogen-con and Polyoxometalates. J. Am. Chem. Soc. 131, 1883-1888 taining heterocycles, phenoxy groups, and combinations (2009). thereof. 0296. 19. Sazou, D. et al. The use of an electrogenerated 10. The process of claim 1 wherein the organic ligand cobalt(I) porphyrin for the homogeneous catalytic reduc corresponds to Formula (1): tion of dioxygen in dimethylformamide. Reactions of (TMpyP)CoII4+ and (TMpyP)CoI3+ where R-L-A-(L-R), (1) TMpyP meso-tetrakis(1-methylpyridinium-4-yl)porphy wherein rin. J. Am. Chem. Soc. 112,7879-7886 (1990). A is a bond or a monocyclic ring or polycyclic ring system; 0297. 20. Adam, W. et al. Selective Reactions of Metal L and each L is a linker moiety; Activated Molecules (Vieweg, Braunschweig, 1992). n is at least 1; and 0298 21. Maurya, M. R. et al. Zeolite-encapsulated cop R and each R is independently a functional group capable per (II) complexes of pyridoxal-based tetradentate ligands of coordinately bonding to at least one metalion. for the oxidation of styrene, cyclohexene and methylphe 11. The process of claim 10 wherein n is at least 2. nyl sulfide. Eur. J. Inorg. Chem. 5720-5734 (2007). 12. The process of claim 10 wherein R and each R is 0299. 22. Martens, J. A. et al. Simple synthesis recipes of selected from among carboxylates, nitrogen-containing het porous materials. Micropor. Mesopor. Mater. 140, 2-8 erocycles, phenoxy groups, and combinations thereof. (2011). 13. The process of claim 10 wherein R and each R is 0300 23. Zhao, D. et al. Triblock copolymer synthesis of selected from among —CO.H. —CSH, NO. —SOH, mesoporous silica with periodic 50 to 300 A pores. Science —Si(OH), —Ge(OH) —Sn(OH), —Si(SH), —Ge(SH) 279, 548-552 (1998). —Sn(SH), —POH, - ASOH, - AsOH, -P(SH). US 2013/018445.6 A1 Jul. 18, 2013

—As(SH), —CH(SH), —C(SH), —CH(NH), and the wavy lines represent the attachment point of the A —C(NH2), —CH(OH), —C(OH), —CH(CN) and ring to the remainder of the organic ligand. —C(CN), —CH(RSH), C(RSH), —CH(RNH), 16. The process of claim 1 wherein the metal comprised by —C(RNH), —CH(ROH), C(ROH), —CH(RCN), the mixture is a metal selected from Group 1, 2, 3, 4, 5, 6, 7, —C(RCN), and combinations thereof wherein each R is 8, 9, 10, 11, 12, 13, 14, 15, and 16 of the Periodic Table independently an alkyl or alkenyl group having from 1 to 5 (according to the IUPAC Group numbering format). carbon atoms, or an aryl group consisting of 1 to 2 phenyl 17. The process of claim 1 wherein the metal comprised by rings. the mixture is a metal selected from the group consisting of 14. The process of claim 10 wherein A is a ring selected the alkali metals, alkaline earth metals, transition metals, from benzene, pyridine, pryridinium, pyrimidine, pyrimi Lanthanides, and Actinides. dinium, triazine, triazinium, pyrylium, boroXine, diboraben 18. The process of claim 1 wherein the metal comprised by Zene, and triborabenzene rings. the mixture is a transition metal. 15. The process of claim 10 wherein A is 19. The process of claim 1 wherein the metal comprised by the mixture is Ag", Al", Au", Cut, Cu, Fe", Fe", Hg", Li", Mn", Mn2", Nd", Ni2+, Ni, Pd?", Pd", Pt?", Pt", TI", Yb2+ or Yb. 20. The process of claim 1 wherein the metal comprised by the mixture is metalion selected from the group consisting of copper, chromium, iron and Zinc ions. 21. The process of claim 1 wherein the supramolecular metal organic material comprises a molecular building block selected from the group consisting of square paddle wheel, octahedral, trigonal, and octahedron molecular building blocks. 22. A process for the preparation of a heterocyclic macro cycle-templated Supramolecular metal organic material com prising (i) preparing a reaction mixture containing a meta lated heterocyclic macrocycle, organic ligands and a metal, the metalated heterocyclic macrocycle coordinating a first metal, (ii) forming a metalated heterocyclic macrocycle-tem plated Supramolecular metal organic material comprising the metal, the metalated heterocyclic macrocycle and the ligands O in the reaction mixture by template-directed synthesis with the metalated heterocyclic macrocycle serving as the tem plate, and (iii) exchanging the first metal coordinated by the metalated heterocyclic macrocycle of the metalated hetero cyclic macrocycle-templated Supramolecular metal organic material with a second metal, the first and second metals being different. 23. The process of claim 22 wherein the heterocyclic mac rocycle is a porphyrin, a porphyrazin, a chlorin, a corrin, or a porphyrinogen. 24. The process of claim 22 wherein the heterocyclic mac rocycle is a metalated porphyrin, a metalated porphyrazin, a metalated chlorin, a metalated corrin, or a metalated porphy rinogen. 25. The process of claim 22 wherein the first metal is cadmium and the second metal is a transition metal.

k k k k k