CA2231706C - Supramolecular laminates - Google Patents

Supramolecular laminates Download PDF

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CA2231706C
CA2231706C CA 2231706 CA2231706A CA2231706C CA 2231706 C CA2231706 C CA 2231706C CA 2231706 CA2231706 CA 2231706 CA 2231706 A CA2231706 A CA 2231706A CA 2231706 C CA2231706 C CA 2231706C
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laminate
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Michael Zaworotko
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SAINT MARY'S UNIVERSITY
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16Clays or other mineral silicates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/049Pillared clays

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Abstract

The present invention is directed to a novel class of polymeric supramolecular laminate compounds based on organic or metal-organic materials, methods of making such compounds and uses of such compounds.
The compounds are synthetic, supramolecular class of organic compounds having a polymeric two dimensional flexible architecture comprising organic and metal-organic materials. The compounds of the present invention are capable of self-assembly into laminated three-dimensional structures and are expandable with the reversible incorporation of a guest molecule within the compound. These novel compounds have widespread applications in the separation of gases, liquids and solutes and may also be used as catalysts.
Furthermore, these compounds are ideal as general absorbents/desorbents for aromatics.

Description

SUPRAMOLECULAR LAMINATES
Field of the Invention Thf; present invention is directed to a novel class of synthetic compounds :5 and more particularly, the present invention is directed to polymeric supramolecular laminate compounds based on organic or metal-organic materials, methods of making such compounds and uses of such compounds.
Background of the Invention 1 n Crystal engineering is a field in which new generations of functional organized molecular assemblies may be rationally developed in the solid state.
Such assemblies may include lamellar, bilayer and monolayer architectures for applications in membranes, meso gens, surfactants and Langmuir-Blodgett (LB) films ( 1 ). It is only from an understanding of the crystalline structural details of 15 such systems that their relationship to specific chemical processes and functions may be ellucidated. Crystal engineering of molecular assemblies also provides a degree of ~;,ontrol over bulk properties that is not inherently present in naturally occurring compounds.
A property of solids that has attracted considerable attention from chemists 20 and crystal engineers is the ability of a solid to adsorb and/or desorb molecules in between the two-dimensional sheets in the crystal structure of the solid. Such molecules are commonly referred to as "guest" molecules and the structure into which they may be adsorbed or dcaorbe~l is commonly referred to as the "host"
Clays, via intercalation between two-dimensional (2D) layers, and zeolites, which 25 contain channels and cavities because of rigid three-dimensional (3D) frameworks, are natural solid prototypes of considerable commercial interest because of their widespread applications in separations and catalysis (5). Some examples of metal-organic (6, 7) and organic (8, 9) :~eolite mimics capable of incorporating organic guests as well as some examples of "organic clay mimics" capable of exchanging metal canons have been developed.
U.S. Patents 4,310,440, 4,440,871 and 4,500,651 describe zeolite-type aluminosilicate and phosphate compounds and their metal substituted derivatives.
These compounds are used in industrial processes such as ion-exchange, separation and catalysis. However, these zeolite-type silicates are not suitable or adaptable for other uses because they cannot be controlled with respect to the shape, size and function of their pores or the type of molecules they can interact with.
Metal-organic solids presently known and used are either one dimensional, two dimensional or three dimensional dense solids having no porosity, or solids made by linkage, between metals and bi-, tri- or tetra- organic ligands about a templating agent which acts to occupy the pores in the crystalline solid. U.S. Patent 5,648,508 discloses such synthetic crystalline metal-organic solids having a microporous structure. However, these three dimensional frameworks are rigid structures exhibiting no flexibility and involve covalent bonding within the molecules.
As such, these structures are not useful for a variety of applications.
Summary of the Invention The present invention is a synthetic approach using crystal engineering to produce a new class of compounds which self assemble into polymers having a laminated structure and which are' structurally related to clays but are inherently hydrophobic because of their chemical nature. The compounds are made using crystal engineering technology to produce both metal-organic and organic zeolite/cla.y mimics.
The novel compounds of fhe present invention are inert, easy to make and flexible. 'they are capable of absorbing and desorbing several different types of guest molecules and as such are superior to any known types of solid or rigid synthetic crystalline structures. L>ue to the flexible structure of these novel compounds they are suitable for ~;everal varieties of applications as compared to
2
-3-synthetic compounds having solid, rigid structures. In addition, the three dimensional molecular- arrangement of the novel compounds of the present invention are predictable with reasonable accuracy which allows for the selection of the type of guest molecule that can bind within the compound. Furthermore, '_> the compounds of the present invention are relatively easy and cost efficient to make and are reusuable.
In accordance with an aspect of the present invention are a synthetic, supramolecular laminate class of organic compounds having a polymeric two dimensional flexible architecture comprising organic and metal-organic clay materials of first row transition metals, wherein the compounds comprise repeating asymmetric units which self=assemble into laminated three-dimensional structures that are expandable with the reversible incorporation of a hydrophobic guest molecule within the compound.
In accordance with another aspect of the present izmention is a synthetic 1 '_. hydrophobic clay compound comprising repeating asymetric units having the formula: [[NRZ.HZ]X[X]y]~ wherein; X is a polycarboxylic acid; R is a substituent selected from the group consisting of hydrogen, an <zlkyl group having 1 to 30 carbon atoms, an aryl group having fr~~m l to 5 phenyl ri~tgs, a benzyl group, a phenylethyl group, a phenyl butyl group, an alkylene group, an ethyl ether and an 2C) alcohol; x and y are present in a ratio of 2:1; and z == 0.
In accordance with another aspect of the present invention is a method for making a compound having a two-dimensional Ilexible architecture comprising reacting a solution of amine with a solution of polycarboxylic acid in a suimblc -~ 3a~-solvent in a ratio of 2: l by volume; and slowly evaporating the solvent to obtain crystals of the compound.
In accordance with yet another aspect of the pres-ent invention is a metal organic clay compound having the formula: [M(L)z~L')~Xh]" wherein M is a first S row transition metal; L is a linear bifunctional ligand; L' is a tern~inal ligand; X
ie r~rnmtarinm a = 1 nr') h ~ ~ 7 nr 2~ anrl n >ll
-4-In accordance with another aspect of the present invention is method of making a metal organic clay compound, the method comprising forming a reacting interface between a metal organic solution and a ligand solution wherein the reaction product forms in the interface and comes out of solution as crystals.
Aromatic compounds for use in the crystallization of such metal organic clay compounds include pure or mixed aromatics which range widely in size and electronic nature. Examples of such aromatics may be selected from but are not limited to nitrobenzene, benzene, toluene, xylenes, anisole, veratrole, naphthalene, methylnaphthalene, and pyrene.
The novel metal-organic and organic salt compounds of the present invention have widespread applications in the separation of gases, liquids and solutes. These compounds may also be used as catalysts. Furthermore, these compounds are ideal as general absorbents/desorbents for aromatics. The compounds also have environmental applications for example in agriculture for crop remediation and for pollution clean up of toxic materials from the air and water. They also have use as photonic, conducting, non linear optic and magnetic materials. Due to the inert and chemically unreactive nature of the compounds they also have pharmaceutical use for example in the delivery of drugs in vivo as well as for use in certain foods as binders for food additives. Finally, these compounds may also be used to bind explosives such as nitroglycerin or TNT.
According to aspects of the invention the guest molecules for use with the compounds of the invention may be selected from the group consisting of nitrobenzene, anisole, veratrole, 1,4-dimethoxybenzene, 1,3,5-trimethoxy-benzene, m-xylene, mesitylene, p-nitroaniline, tetramethylene, pentamethylbenzene, hexamethylbenzene, dibenzylamine, naphthalene, 1-methylnaphthalene, pyrene, tetracyanoethylene, tetrathiafulvalene, ferrocene, drugs, food additives, water pollutants, air pollutants, explosives, fluorescent molecules, pheromones, phosphorescent molecules or nonlinear optic active molecules.

-4a-Brief Descriution of the Drawings A detailed description of the preferred embodiments are provided herein below with reference to the following drawings in which:
Figure 1 shows a scheme depicting various possible layered structures that are designed using primary or secondary alkylammonium salts of trimesic acid.
Figure 2 shows the two dimensional hydrogen bonding network observed in compounds 1-4: 1, [N,N-dipropylammonium]Z[HTMA]; , [N,N-dihexylammonium]2[HTMA]; 3, [N,N-dioctylammonium]Z[HTMA]; and 4, [N,N-dihexylarnmonium]2 [HTMA] } . Five different hydrogen bonds are marked (shown as dashed lines, a-e, Table 1). The alkyl substituents of the ammonium cations are omitted for clarity. N and 0 atoms are shown as hatched and filled circles, respectively. The dotted lines are: marked on the sheet to show the alternating columns of alkyl subsituents.
Figure 3 shows perspective views of the structures of compounds 1 to 4 (a-d of table 1): 1, [N,N-dipropylammonium]2[HTMA]; 2, [N,N-dihexylalnmonium]2[HTMA]; 3, [N,N-dioctylammonium]2[HTMA]; and 4, [N,N-dihexylarnmonium]2[HTMA] }
Figure 4 shows the interdigitated mixed supramolecular laminate structure of compound 5: [N,N-dibenzylammonium] [N,N-dipropylammonium] [HTMA].
Layer A contains N,N-dibenzylarnmonium and N,N-dipropylammonium cations.
Layer B contains dibenzylammonium canons only. Methyl alcohol is involved in the hydrogen bonding in layer B.
Figure 5 shows the hydrogen bond networks in [N(benzyl)2H2]2[HTMA]
(mesitylene guest), benzyl groups are omitted for the sake of clarity;
Figure 6 shows the structure of a supramolecular laminate prepared from a primary alkylammonium cation, phenethylammonium.
Figure 7 shows the hydrogen bond networks in [N(benzyl)2H2]2[HTMA]
(veratrole guest), benzyl groups are omitted for the sake of clarity;
Figure 8 illustrates three modes of crystal packing in supramolecular laminates based upon [N(benzyl).2H2]2[HTMA] and [N(benzyl)2H2]2[HTML].
Guest molecules are in space-filling mode: Figure 8(a) shows a flat structure in which adjacent layers and guests are identical, [N(benzyl)2H2]2[HTML] ~ 1.5 p-dimethoxybenzene; Figure 8(b) shows a flat sheet in which guest molecules have alternating packing modes, [N(benzyl)2H2]2[HTML]~ 1-75nitrobenzene, triclinic, Figure 8(c) shows a corrugated sheet in which adjacent layers and guests are identical, [N(benzyl)2H2]2[H:TMA] ~ veratrole~;
5 Figure 9 shows a second embodiment of the present invention. Shown is a view of taro stacked grids in the metal organic compound la, [Co(4,4'-bipyridine)2(N03)2]n. The benzene guest molecules (black) engage in stacking interactions with the 4,4'-bipy ligands of the square grid networks and with other benzene molecules; and Figure 10 shows perspective and overhead views of the structure of compound lc, [Co(4,4'-bipyridine)2(N03)2Jn. The square grid is presented in space-filling mode whereas the guest molecules are presented in cylinder mode.
In l:he drawings, preferred embodiments of the invention are illustrated by way of example. It is to be expressly understood that the description and drawings are only for the purpose of illustration and as an aid to understanding, and are not intended ass a definition of the limits of the invention.
Detailed lDescription of the Preferred Embodiments 1 S The present invention provides a novel, synthetic, supramolecular class of organic compounds having a polymeric two dimensional flexible architecture expandable with the reversible incorporation of guest molecules. These compounds comprise both metal-organic and organic materials which are capable of self assembly into laminated three dimensional structures and have an affinity for intercalation with guest molecules without affecting their structure. As such they are ideal for a wide variety of applications most notably as general adsorbents and desorbents of a myriad of organic compounds and gas molecules.
For the purpose of the present invention, "two-dimensional" refers to flat sheets containing metal-ligand bands or charge assisted hydrogen bonds in the first two directions, whereas "three-dimensional" refers to weak forces in the third direction present between laminated sheets. The term "flexible" as used herein means conformationally flexible, that is, there are many possible orientations of the host framework. As used herein, "guest molecule" refers to the molecule which lies in between the two-dimensional laminated sheets of the compound which
6 preferably is an organic molecule. "Intercalation" or "intercalated" as used in the present invention refers to placement in between laminated layers of the compound, whereas "interdigitation" refers to substituents on the host framework arranged i.n such a way that the head of one substituent sits beyond the head of the group above. This resembles a "zipper formation" and is clearly shown in Figure 1. Intercalated guest molecules push the layers of the host framework apart.
It is understood that crystallographic methods and terminology may be used herein that is well known to those skilled in the art of supramolecular synthesis and compound crystallography.
In a first embodiment of the present invention, there is provided a novel class of synthetic compounds having a two dimensional hydrogen bonded motif which forms lamellar crystalline structures due to the presence of strong hydrogen bonds between complementary organic cations and anions. These synthetic lamellar clays are hydrophobic and can be made to have an entire three dimensional molecular predictable arrangement, with reasonable accuracy, due to the hydrosphobic interactions between interdigitated alkyl or aryl groups in the third dimension.
The compound comprises repeating asymetric units having the formula:
[[NR2H2][X]]2 wherein: X is a polycarboxylic, acid; R is a substituent selected from the group consisting of hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having from 1 to 5 phenyl rings, a benzyl group, a phenylethyl group, a phenylbutyl group, an alkylene group, an ethyl ether and an alcohol; :~ and y are present in a ratio of 2:1; and z > 0. These synthetic hydrophobic clay compounds preferably comprise primary or secondary 2.5 ammoniwm salts of polycarboxylic acids.
Polycarboxylic acids are suitable templates for the generation of two dimensional hydrogen bonded arrays. Suitable polycarboxylic acids for use in the present invention are both saturated and unsaturated organic aromatic acids having at least three carboxylic groups. Preferred acids for use in the present invention are
7 trimesic acid (H3TMA, 1,3,5-benzenetricarboxylic acid, herein referred to as HTMA), trimellitic acid {H3TMh, 1,2,4-benzenetricarboxylic acid, C9H606~
herein referred to as HTML) and naphthalene tricarboxylic acid. All of these acids for use in the present invention are inexpensive and thermally and chemically robust polycarboxylic acids having exodentate functionality in two dimensions meaning that the active functional groups are arranged outside the outside of the molecule .and point away from the center.
The process of the invention used to make the crystalline organic salts is based on deprotonating salts of polycarboxylic acids such as for example saturated or unsaturated aromatic acids having at least three carboxylic groups. These are reacted wiith amines to afford salts with flat hydrogen bonded sheet structures.
These rigid hydrogen bonding patterns are robust and the presence of ammonium canons in the sheet makes such structures ideal for designing interdigitated supramole;cular lamellar structures since long chain groups such as for example alkyl groups can be substituted at the ammonium moiety. For example, [NR2H2],>[HTMA] and [NR2H2),[HTML]2 are synthesized in a simple processes by the app>ropriate acid-base reaction in a solvent such as methyl alcohol, ethyl alcohol or water. These compounds exhibit their resultant laminate structures because of the complementary nature of the strong hydrogen bond donors of the cations and the strong hydrogen bond acceptors of the anions. When R = propyl, hexyl, octyl or decyl groups, the resultant laminates poorly incorporate guest molecules. However, it is now demonstrated that when R = benzyl, for example, interdigita~tion is eschewed in favour of incorporation of solvent or aromatic guest molecules.
X-ray crystallographic characterization of several host-guest complexes based upon [N(benzyl)2H2]2[HTMA] or [N(benzyl)2H2]2[HTML] hosts revealed that aromatics as divergent in size: and electronic character as nitrobenzene, anisole, veratrole, 1,4,dimethoxybenzene, 1,3,S,trimethoxybenzene, m-xylene, mesitylen~e, tetramethylbenzene, pentamethylbenzene, hexamethylbenzene,
8 dibenzylamine, naphthalene, 1-methylnaphthalene and pyrene can be incorporated as guests by intercalation. It is understood by those skilled in the art that guests suitable for intercalation into the compounds of the present invention are not limited to the guest molecules listed herein, but may also include other guest molecules selected for specific applications of the compounds. For example, such suitable guest molecules may include but are not restricted to explosives, fertilizers.. pheromones and pharmaceutical agents.
Figure 1 depicts various possible layered structures that may be designed using secondary alkylammonium salts of trimesic acid. The crystal structures of compounds 1-4: l, [N,N-dipropylammonium]2[HTMA]; 2, [N,N
dihexylanlmonium]2[HTMA]; 3, [N,N-dioctylammonium]2[HTMA]; and 4, [N,N-dihexylammonium]2[HTMA] exhibit identical two dimensional hydrogen bonding networks stabilized by N+-H...O- and O-H... O- hydrogen bonds as shown in Figure 1. 'Table 1 is a compilation of hydrogen bond lengths of compounds 1-4 and demonstrates that the relevant hydrogen bond lengths are almost identical in each of the compounds.
The ammonium protons in the sheet are engaged in a robust hydrogen bonding network and are arranged in alternating columns (Figure 1 ). The hydropholbic alkyl substituents of~the ammonium canons project above and below the sheet and the space between the protruding columns of alkyl groups facilitates interdigitation or close-packing of the adjacent layers (Figure 2). The geometrical arrangement of the cations in the layer is critical and controls the stacking in the third direction. The interlayer separations of compounds 1-4 are approximately 7.0~,, 10.3., 12.4., 14.6,, respectively, and are directly related to the alkyl chain lengths and the interdigitation of the alkyl groups that facilitate close packing.
There is a recognizable tilt in the octyl and decyl chains of compounds 3 and with respect to the surface of the sheet (77.2 ° , 73.9 ° ), especially when compared to that seen for the propyl and hexyl groups in compounds 1 and 2, respectively (87.4 ° , 89.0 ° ). The dimensions of the repeating unit of the plane are
9 approximately 16.9. x 21.6. in all four compounds, but only correspond to unit cell parameters i.e. the be plane, in compounds 3 and 4.
A mixed cation supramolecular laminate of HTMA with N,N-dibenyzlammonium and N,N-dipropylammonium has also been synthesized and is herein refc;rred to as compound 5 (Scheme lb, Figure 1). Compound 5 is a doubly deprotonated salt, the asymmetric unit containing four anions, six N,N-dibenzylammonium cations, two :L~1,N-dipropyl ammonium cations and one molecule of methyl alcohol. The crystal structure reveals an interdigitated supramole;cular laminate architecture with alternating layers of different 1 ~0 composition (Figure 3). The hydrogen bonding pattern of layer A, a mixed canon supramole:cular laminate, is similar to that present in compounds 1-4 (Figure 1).
However, layer B, which contains dibenzylammonium canons, has a slightly different hydrogen bonding pattern as the methyl alcohol molecule is also involved in the hydrogen bonding scheme. This observation suggests that a wide range of 1 S new supramolecular laminates is now achievable, and that is now possible to generate such laminate compounds exhibiting interesting properties such as liquid crystallinity and the ability to intercalate guest molecules.
It is demonstrated that the connectivity of the hydrogen bonding networks that occurs within the laminates of HTMA salts does not change if the guest 20 molecule us different (Figure 5). The hydrogen bond network with the HTML
salts (Figure 7) is also invariable with the set of HTML salts thus synthesized.
Furthermc>re, the networks in both HTMA and HTML salts are adaptable enough to permit at least three crystal packing modes: corrugated sheets, flat sheets with identical adjacent layers and guest environment; flat sheets with alternating layers 25 and guest environment. These structures are exemplified in Figures 8A, 8B
and 8C.
In most of the compounds the proportion of guest varies from 16.6% to 26.3% by mass of the compound and is based upon the relative size of the guest molecule and the packing mode adapted by the laminate compound. The unit cell lengths in these compounds are based upon multiples of approximately 12A. x 17~.
x 21 ~.. The 12A distance represents the approximate interlayer separation whereas 17~. x 21~~ represents the dimensions of the repeat unit within the laminate (Figure 5). An analogy might reasonably be drawn between the new compounds and lipid bilayers since the former are effectively an infinite stack of hydrophobic bilayers.
The interactions between guest molecules and the host frameworks are based upon a plethora of edge-to-face and face-to-face interactions between various aromatic moieties. In the absence of pest molecules or the presence of a very small number of guest or solvent molecules interdigitation of benzyl groups occurs and interplanar separations are reduced to 8-9A.
The results with monoalkylammonium salts are similar to those just described.. For example, when R2=H, benzyl, H, phenylethyl or phenylbutyl, structures based upon alternating hydrophobic and hydrophilic layers are obtained.
An example of such a structure is 8[HTMA]16[H-phenylethylamine]2,1OH20, and is illustrated in Figure 6. This compound contains an asymmetric unit having organic residues and 10 water molecules and crystallizes in space group P 1.
The formula of this compound is C328H372058N16 representing a supramolecular bilayer. Other compounds of the present invention include but are not restricted to C21H36~~206~ C33H60N206~ C41H76N206~ C49H92N206 ~ C133H148N8025 and C200H244N16058.
There are two important observations with respect to these supramolecular compounds. First, the inherent torsional flexibility of the R2 groups such as benzyl and the agility of even strong hydrogen bonds to distort are manifested by generation of a number of cavity and/or channel geometries. The ability of these supramolc;cular laminates to form similar crystalline structures with such a wide range of guests is therefore rationalized. Second, the guest molecules can be easily removed by heat or vacuum to afford a stable amorphous apohost or exchanged by contact with solvent that is rich in another guest molecule. When combined with the low cost, facile supramolecular synthesis, chemical stability and modular nature, these novel organic compounds have several potential applications in the context of separations, sensors and general purpose adsorbents/desorbents.
In accordance with a second embodiment of the present invention are synthetic two dimensional square grid polymers comprising metal-organic materials. These polymers are analogous with clay minerals in that they exhibit intercalation capabilities in the presence of aromatic compounds and are based upon square planar or octahedral metals and linear spacer ligands. These compounds are inexpensive, air/moisture stable, and easy to prepare. These compoundis are also polymeric two dimensional flexible architectures and may l0 self assemble into laminated structures.
Thf;se metal organic clay compounds have the formula: [M(L)2(L')aXb]n wherein Nf is a first row transition metal; L is a linear bifunctional ligand;
L' is a terminal ligand; X is a counterion; a = 1 or 2; b = 1, 2 or 3; and n > 0.
Suitable metal ions for use in the compound are divalent or trivalent metals having an 1:5 octahedral or square planar metal center. Preferable first row transition metals are Co, Ni, Cu and Zn. The linear bifuntional ligands may be selected from 4, 4'-bipyridine and its extended versions such as bis(4-pyridyl)ethane. Terminal ligands suitable for use in the compound of the present invention may include water, ammonia and pyridine. Suitable counterions may include N03, Cl, S04, 20 SiFg and PF6.
Thc;se metal organic clay compounds are crystallized by adlayering metal organic solutions with a selected ligand solution. The adlayered solutions create a reactant interface after a period of time in which the reaction products (crystals) are produced .at room temperature. The formed crystals of the compound fall out of 25 solution and are then separated for use in various applications. If the solutions are not carefully adlayered then amorphous powdered materials of the same compound are obtained. Suitable metal organic solutions for use in the method of the present invention may include but are not limited to Co(N03)2-6H20 in methyl alcohol and Ni(NO3)2-6H20 in methyl alcohol. The ligand solution is preferably 4,4'-bipyridine or one its derivatives in a suitable solvent such as an alcohol, benzene, chlorobenzene or naphthalene. Preferred metal organic clay compounds of the present invention are [Co(4,4'-bipyridine)2(N03)2]n and [Ni(4,4'-bipyridine~)2(N03)2]n ,where n>0.
Crystallization of [Co(4,4'-bipyridine)2(N03)2~n in the presence of guest molecules such as benzene, chlorobenzene or naphthalene forms the compounds [Co(4,4'-t>ipyridine)2(N03)2]n -2benzene (la), [Co(4,4'-bipyridine)2(N03)2]n -2chlorobenzene ( 1 b) and [Co(4,4'-bipyridine)2(N03)2]n -3naphthalene ( 1 c), respectively. Crystallization of [Ni(4,4'-bipyridine)2(N03)2]n in the presence of chlorobenzene or naphthalene guest molecules forms the compounds [Ni(4,4'--bipyridine:)2(N03)2~n -2chlorobenzene (2b) and [Ni(4,4'-bipyridine)2(N03)2]n -3naphthalene (2c), respectively. All five compounds were characterized by single crystal x-ray crystallography, the results of which indicate that the respective guest molecules are complementary with the square grid framework. Figure 9 reveals how the guest benzene molecules in compound (la) form edge-to-face and face-to-face interactions with the hydrocarbon portion of the 4,4'-bipyridine moieties and between themselves. These interactions are presumably a driving force for the clathration of the guests and a major mitigating factor against interpenetration.
It is understood by those skilled in the art that the type of guest molecules for use with the metal organic clay compound of the present invention is not limited to benzene, chlorobenzene or naphthalene but may also include for example nitrobenzene, toluene, xylene, anisole, veratrole, methylnaphthalene, 1,2-dimethoxybenzene, pyrene and mixtures thereof. Other molecules may also be used as guest molecules in the metal organic clay compounds and may be selected depending on the desired application of the compound. Suitable guest molecules may be selected from but are not limited to pharmaceutical agents, pheromones, explosive chemicals and food additives.

The five compounds (la,b,c, 2a, b) all crystallize in space group C2/c and they have two unit cell parameters in common, i.e. approximately 12A x 22A.
However, the crystal packing in (la), (lb) and (2b) is quite different from that in (lc) and (2c). In the case of the former compounds, the square grid layer does not align with a unit cell face and adjacent layers are slipped in one direction by approximately 20%, i.e. every sixth layer repeats. In the case of the latter compounds, the interlayer separation is large enough that layers are almost eclipsed. These observations suggest that, although the dimensions of the square grids are independent of both metal and guest, interlayer attractions are so weak that the guest molecules determine the interlayer separation. Indeed, the interlayer separations vary from 5.9A to 8.0 A in the compounds reported herein (Table 2).
Intralayer structure is similar in all compounds with M-N and M-O distances being within expected ranges. Tables 3 and 4 reveal the features of 19 additional square grid polymers based on [M(4,4'-bipyridine)2(N03)2]n, where M is selected from Co or Ni.
In compounds (Ic) and (2c) a larger amount of a larger guest is held than in compounds (la), ( 1 b) and (2b). Indeed, for compounds (lc) and (2c) the proportion of the crystal that is occupied by guest molecule is 44% by weight and an even larger percentage by volume. However, as Figure 10 reveals, the third naphthalene guest molecule sits comfortably inside the square grid.
Naphthalene is roughly rectangular but the cavity is able to adapt because one pair of bipyridine molecules lies flat whereas the other orients vertically. The remaining naphthalene molecules form an infinite stack via edge-to-face interactions similar to those seen in pure naphthalene (Figure 10).
In terms of guest:host stoichiometry and crystal packing of the square grids there are three types of compound. Type A compounds are isostructural with one another. 'they crystallize in space group C2/c with similar cell parameters, they have 2:1 ~;uest:host stoichiometry and they have interplanar separations of approximately 6A. In these compounds the guest molecules form edge-to-face and face-to-face interactions with the hydrocarbon portion of the 4,4'-bipyrimide moieties and between themselves. The crystal packing of the square grids in type A compounds appears to be influenced by C-H...O hydrogen bond interactions between 4,4'-bipyridine ligands of one square grid and nitrates of the adjacent square grid. These interactions occur in all of the compounds that display the type A crystal packing. Pairs of nitrate groups adapt an orientation consistent with 2-fold or inversion symmetry and can therefore be regarded as being trans- to one another. Interplanar separations do not vary significantly within the scope of type A compounds as seen in Table 3. The square grids do not align with a unit cell face and adjacent grids are slipped in one direction by approximately 20%, ie.
every sixth layer repeats.
Type B compounds have a somewhat larger interlayer separation but there is still C-H...O hydrogen bonding between 4,4'-bipyridine ligands and nitrate ligands of adjacent grids. The positioning of grids is different and facilitates the 1.5 inclusion of one guest molecule in the center of each grid and a larger interlayer separation (Table 3). The other guest molecules) lie between the grids and engage in stacking; interactions with the 4,4'-bipyridine ligands and themselves.
This is exemplified by compounds ( 1 i) and (2i). Type B compounds differ from type A
compounds in the orientation of the nitrate ligands and the way in which adjacent layers stark. Nitrate ligands on adjacent layers form O...H-C hydrogen bonds with 4,4'-bipyridine ligands on adjacent layers in such a manner that larger interplanar separations are facilitated. The nitrate ligands are orientated on the same side of the metal in a cis-type arrangement. There is less uniformity in the crystal packing in type B compounds.
Thc: crystal packing in type C compounds is also controlled by weak interactions between adjacent layers and is a hybrid of the type A and type B
compounds. Intralayer structure is similar in all 19 compounds (Tables 3 and 4) with M-N and M-O distances being withing expected ranges and C-H..O
interactions between nitrate groups and 4,4'-bipyridine ligands. Each of type A, B

and C compounds contain hydrophobic cavities within the grid. Furthermore, these cavities are flexible since the bridging ligands have conformational flexibility around the M-M vector. The cavities can therefore either be square or rectangular, or, if therf; is distortion around the ligand-metal-ligand angle, then the cavities may be rhombic.
To summarize, a supramolecular synthetic approach using crystal engineering has been used to produce a new class of compounds which self assemble into three dimensional laminated polymers which are structurally related to clays but are inherently hydrophobic because of their chemical nature.
These new compounds include both metal-organic and organic zeolite/clay mimics.
These compounds are inert, easy to make and flexible. They are capable of absorbing and desorbing several different types of guest molecules and as such are superior to any known types of solid or rigid synthetic crystalline structures. Due to the flexible structure of these novel compounds they are suitable for several varieties of applications. In addition, the molecular arrangements of these compounds are predictable with reasonable accuracy which allows for the selection of the type of guest molecule that can bind- within the compound. It is understood that guest molecules for interdigitation or intercalation with the compounds of the present invention can vary widely with respect to the type of guest molecule and its size. As the compounds can be specifically designed with respect to the crystal packing structure and size it is comprehendible that a novel compound within the scope of t:he present invention can be designed for almost any type of guest compound and can be used in a wide variety of applications.
In the case of both organic and metal-organic compounds, guest molecules can be easily removed by heat and/or vacuum to afford a stable amorphous apohost compound or exchanged by contact with solvent that is rich in another guest molecule. For this reason, these compounds have potential applications in the context of separations (e.g. as solid filters or membranes for separations of enantiomers or isomers), sensors (as bulk powders or as films), as general purpose adsorbents (e.g. for aromatics from aqueous feeds or volatile organics from polluted air in the context of environmental remediation; stabilization of unstable molecules such as fuels and explosives; or as adsorbents for sensors, in particular for aromatics) and/or desorbents (e.g. for crop control via controlled release of :5 pheromones, for oral drug delivery). These compounds may therefore also be used in the conl:ext of heterogeneous catalysis (reagents adsorb, products desorb), solid-state synthesis such as photochemistry (reagents are trapped in fixed orientation, reaction occurs, pure product desorbs), separations media including chiral porous solids (laminate is chiral by nature or because of enantiomeric substituent), l n materials science applications such as NLO, magnetism and liquid crystallinity.
For use as a catalyst, the compound can greatly accelerate the rate of reaction between two or more reactants while itself being unconsumed.
Compounds of the present invention can be designed as a catalyst for specific reactions as the metal that sustains the polymer could be chosen for its known 1:5 Lewis Acid or redox activity. Reactions for which compounds of the present invention may be designed for may include but are not limited to the cracking of hydrocarbons and related industrial chemical reactions involved in petroleum refining and synthetic organic chemical manufacturing.
The; structural nature of the organic compounds makes them amenable to the 20 property of liquid crystallinity. Many of the compounds with long chain alkyl substituents show multiple phase and/or colour changes before their melting point.
As a liquid crystal the compounds resemble liquids in certain respects such as viscosity and crystals in other properties such as light scattering and reflection. As such they may change colour in response to atmospheric changes such as in 2:5 temperature when utilized in certain applications. Uses of such liquid crystals may be in TV and electronic display tubes, LED displays, electronic drives in clocks and calculators, integrated circuit inspection and other devices.

The metal organic compounds have the potential to be used for magnetic applications. The compounds of the present invention may be used as magnetic separators in which a magnetic field is used to remove particulates from the compounds. The compounds of the present invention are inherently paramagnetic if M is a paramagnetic metal moiety and they have preordained connectivity between adjacent metal centers.
With respect to use of these compounds to desorb/adsorb guest molecules, this is accomplished at varying rates depending upon the host structure and the guest molecule structure. These compounds therefore have the potential to be used as they arc: or in combination with a polymer membrane or as films on surfaces. In all cases the synthetic laminated compounds are made in the presence of a suitable guest which is subsequently removed. The resulting compound then behaves like a clay and adsorbs, via intercalation, a wide range of neutral organic guest which are not limited by size or electronic structure. The compound can be used to adsorb toxic materials from polluted waste streams or air. Alternatively, due to the inert and non toxic nature of the present compounds, they can be incorporated with a guest for slow release in such applications as drug delivery or pheromone release both in vivo and in vitro. The laminate compound itself is recyclable as it is insoluble in water and common organic solvents and thermally stable to at least 220°C.
The laminate compounds also have use in nonlinear optics by the incorporation of guest molecules which are highly polarizable such as p-nitroaniline. For example, many of the organic host frameworks are inherently polar by nature and they would therefore be expected to induce parallel disposition of guest molecules. For use as a conductive or magnetic material, the metal-organic laminate compounds can be designed to inherently have such properties as part of the: host framework or alternatively, organic compounds can be designed using guests such as pyrene, tetracyanoethylene and tetrathiafulvalene. The organic laminate compounds can also be used as liquid crystals when designed with long alkyl chains.
Both classes of compound may be used as precursors for the generation of new covalently bonded polymeric materials. In many cases, simply heating the laminates until they chemically react will afford two or three dimensional covalent polymers with structures and composition based upon the laminate and its guests.
Experimental Procedures Example 1 - Preparation of HTMA Salts The series of dialkylammonium salts, [N,N-dipropylammonium]2[HTMA], l, [N,N-dihexylammonium]2[HTMA], 2, [N,N-dioctylammonium]2[HTMA], 3 and [N,Ndidecylammonium]2[HTMA], 4, were synthesized by slow addition of 2 equivalents of the appropriate amine to one equivalent of H3TMA in methyl alcohol anal, in order to prevent precipitation of non-stoichiometric products, refluxing for 2 hours. Quantitative yields of the colorless solids of compounds 1-4 were obtained by slow evaporation of MEOH. Crystals of compounds 1 and 2-4 suitable for single crystal X-ray crystallography were obtained from 1-butanol and MEOH, respectively (1, m.p. >300°C; 2, m.p. 243°C; 3, m.p.
248°C; 4, m.p.
265°C).
Crystal Data for salts of compounds 1-S: (1) C21H36N206~ monoclinic, P21/c, a+8.734 (3), B=16.951(7), c=17.811(7), f3=103.99(4)°, V=2558.70(14)A3, Z=4, D~ 1.07 Mgm-3. 1427 reflections out of 3349 unique reflections with I>2.Sa were considered, final R-factors Rf=0.083, Rw 0.068 (2) C33H6pN2O6, monoclinic, P21/n, a=11.531(3), b=16.942(2), c+19.952(6), I3=98.07(3)°, V=3859.2(16)A3, Z=4, D~ 1.00 Mgm-3. 1339 reflections out of 5042 unique reflections with I>2.56 were considered, final R-factors R f=0.090, Rw=0.086. The data for 1 and 2 were measured on an Enraf Nonius CAD-4 diffractometer at 290K using the w scan mode.

(3) C41H76N206, monoclinic, P21/c, a=12.4771(7), b=16.8788(9), c=21.5789( 11 ), !3=91.992( 1 ) ° , V=4541.7(4)A3, Z=4, Dc=1.01 Mgm-3.

reflections out of 6333 unique relections with L3.0a were considered, final R-factors R f=0.114, Rw 0.1 O 1.
S (4) C49H92N2~6~ monoclinic, P2l/c, a=14.6856(8), b=16.8941(11), c=21.592(13), !3=97.970(2)°, V=5305.5(6)A3, Z=4, D~ 1.01 Mgm-3. 2064 reflections out of 4291 unique reflections with I>3.Oa were considered, final R-factors R f=0.117, Rw=0.115.
(5) C133H148N8~25~ monoclinic, P21, a=16.7901(3), b=16.8905(2), c=21.9464(2), f3=96.384(1), V=6185.3(4), Z=2, Dc=1.211Mgm-3. 18350 reflections out of 20242 unique reflections with I>4.06 were considered, final R-factors R f=0.083, Rw 0.086.
The intensity data for 3-5 were colected on a Siemens SMART/CCD
diffractometer at 173K using the 8 scan mode. The temperature factors for the terminal C atoms in the alkyl chains of 1-5 are high, probably a manifestation of unresolvable disorder, and account for the relatively high R-values. Atomic coordinates, bond lengths and angles, and thermal parameters have been deposited at the Cambridge Crystallographic Data Centre (CCDC).
Modes of Crystal Packing in [N(benzyl)ZH2JZ[HTMA]
and N benzyl) HZIzLHTML1 Compounds Figure 8 illustrates three modes of crystal packing in supramolecular laminates based upon [N(benzyl)2H2]2[HTMA] and [N(benzyl)2H2]2[HTML].
Guest molecules are in space-filling mode: Figure 8(a) shows a flat structure in which adjacent layers and guests are identical, [N(benzyl)2H2]2[HTML] ~ 1.5 p-dimethoxybenzene, orthorhombic, space group Aba2, a= 21.414(1), b=17,161 ( 1 ), c = 24.05 1 ( 1 )A, V= 8840.4(9)A3, Z = 8, p = 1.22 Mgm-3, R= 0.086, Rw = 0.113 for 4670 out of 9675 reflections with 1>26(I); Figure 8(b) shows a flat sheet in which guest molecules have alternating packing modes, [N(benzyl)2H2]2[HTML]~ 1-75nitrobenzene, triclinic, space group P-1, a = 17.089(1), b=21.417(1), c =24.602(2)A, a 106.568(1),1 = 95.664(1), y= 90,405(1) ° , V =
8582.4(9)A3, Z=8, p = 1.27 Mgm-3, R = 0.084, Rw = 0.2039 for 15223 out of 36581 reflections with 1>26(I); Figure 8(c) shows a corrugated sheet in which adjacent layers and guests are identical, [N(benzyl)2H2]2[HTMA] ~ veratrole~ 1/3EtOH, monoclinic, space group P21/c, a 11. 5765(6), b = 49.905(3), c = 21- 505(1)A, 13=90.929(1) °, V =
12423(1)A3, Z = 12, p = 1.22 Mgm-3 , R - 0.076, Rw = 0.139 for 11030 out of 21508 reflections with 1>2~(I). Data were collected on a Siemens SMART/CCD
diffractometer at 193K and structures were solved and refined using SHELX/TL;
Example 2 - Synthesis of Metal Organic Compounds Compound la: A solution of Co(N03),-6H20 (0.14 g, 0.48 mmol) in MEOH (20m1) was added to a solution of 4,41-bipyridine (0.23 g, 1.5 mmol) in benzene (20m1). After standing at room temperature overnight, pink crystals of la 1:5 were obtained (yield: 0.16 g, 0.24 mmol, 51 %). The presence of the benzene molecules was confirmed by IR spectroscopy. When removed from the presence of mother liquor, crystals become opaque and lose crystallinity within minutes.
Compound 2b: A solution of Ni(N03)2-6H20 (0-14 g, 0.48 mmol) in MEOH (20 ml) was added to a solution of 4,4'-bipyridine (0.23 g, 1.5 mmol) in chlorobenzene (20 ml). After standing at room temperature overnight, light aqua green crystals of 2b were obtained (yield: 0.28 g, 0.39 mmol, 82%). The presence of chlorobenzene in the bulk material was confirmed by IR spectroscopy.
Crystals exposed to the atmosphere become opaque and lose crystallinity within several hours. TGA analysis reveals the following: 32% weight loss from 81 °C
to 162°C.
This data suggests loss of 2 moles of chlorobenzene. Above 162°C, there is further decomposition. Crystals of lb were obtained in the same manner (yield 0.25g, 730g).

Compound 2c: A solution of Ni(N03)2 6H20 (0.14 g, 0.48 mmol) in MEOH (20m1) was added to a solution of 4,4'-bipyridine (0.23 g, 1.5 mmol) and naphthalene (0.62 g, 4.8mmo1) in MEOH (20m1). Aqua blue crystals of 2c were obtained overnight and were collected by filtration (yield: 0.31 g, 0.36 mmol, %). The presence of the guest molecules was confirmed by IR spectroscopy.
Crystals exposed to the atmosphere become opaque within hours. Crystals of 1 c were obtained in the same manner (yield 0.16g, 39%). TGA analysis of 1 c revealed the following: 51.71 weight loss between 1000°C and 2100°C, a further 38.8% weight loss between 210°C and 320°C and no further weight loss up to 450°C. These weight losses and IR spectroscopy suggest that these changes correspond to: loss of naphthalene and N02; loss of 4,4'-bipyridine leaving a residue of Co304. Similar results were obtained for 2c.
Example :3 - X-ra~r~stallo~raphy - Metal Organic Compounds la,b,c, 2a,b X-ray data for compound la: 0.2 x 0.3 x 0.4 mm pink rectangular crystal, monoclinic, C2/c with a 21.3256(3), b = 11.5305(1), c = 12.6079(2) A, l3 =
100.
767 (1) °, Z = 4, V = 3045 .64 (7) A3, _- pcalc = 1. 42 Mgm-3, ~. =
0.61 mm-1, 2.0>26>53.0 ° , T = 173K.
X-ray data for lb: 0.1 x 0.15 x 0.4 mm, pink rod shaped crystal, monoclinic, C2/c with a = 21.8140( 12), b 11.5281 (2), c 12.8767 (7) A, l3= 102.674 ( 10) ° , Z =
4, V - 3159.3 (3) A3, pcalc = 1.52 Mgm-3, p. = 0.76 mm-1, 2.0>26>54.0°, T
290K.
X-ray data for lc: 0.20 x 0.40 x 0.40 mm, pink parallelpiped crystal, monoclinic, C2/c with a = 16.1658(20), b = 11.4940(16), c = 22. 855 (4) A, 13 96.
73 (3) ° , Z = 4, V = 4217.4 ( 10) A3, 2.0>26>49.9 ° , T = 290K.
X-ray data for 2b: 0.15 x 0.15 x 0.3 mm, pale blue rod shaped crystal, monoclinic, C2Ic with a = 21.678(3), b == 11.4111(10), c=12.9139(16) A, !3 =
103.401 (l l) °, Z = 4, V = 3107. 5 (7) A3, pcalc = 1. 54 Mgm-3, ~ =
0.85 mm-1, 2.0>26>49.8 ° , T = 290K.

X-ray data for 2c: 0.15 x 0.30 x 0.30 mm, pale blue plate, monoclinic, C2/c with a = 16.1014(8), b = 11.3812(6), c = 22.6453(11) A, 13 = 97.306(11)A, Z=
4, V
= 4116.1(4) A3, pcalc = 1. 42 Mgm-3, ~ = 0.53 mm-1, 2.0>26>53.0 °, T =
290K.
Data were collected on Siemens SMART CCD (la, lb, 2c)or Enraf Nonius .'> CAD-4 ( 1 c, 2b) diffractometers with Moka radiation (~, = 0.70930 A) using the 6/26 or w/26 scan modes, respectively. Structures were solved by direct methods and refined using the PC version of the NRCVAX system. Non-hydrogen atoms of the coordination polymer and guest molecules were refined with anisotropic thermal parameters. The naphthalene molecules that sit inside the square grid in lc and 2c were observed to have significantly higher thermal motion than other guest molecules. The following values were obtained: la, R = 0.039, Rw = 0.049, 2613 out of 3177 reflections with I > 4.0 6(I) and 206 parameters; lb, R 0.058, Rw, _ 0.075, 2425 out of 2791 reflections with I > 3.0 6(I) and 215 parameters; lc, R =
0.054 and Rw = 0.056 were obtained for 2730 out of 3614 reflections with I >
2.5 1.'i ~(I) and 31)5 parameters; 2b, R = 0.054, Rw = 0.056, 2186 out of 2739 reflections with I > 3.0 6(I) and 215 parameters; 2c, R = 0.078, Rw = 0.109, 3203 out of reflections with I > 4.0 6(I) and 251 parameters. Hydrogen atoms of the 4,4'-bipyridine moieties and guest molecules were placed in calculated positions with dC_H, = 1.00 A. Residual electron density (min./max., eA-3): -0.88/0.87, -1.31/1.17, -0.43/0.35, 1.17/1.08 and -0.66/0.60 for la, Ib, lc, 2b and 2c, respectively.

Table 1: Hydrogen Bonding Distances (A) in the 2D Layers of Compounds 1-5 O...O N...O
a b c d a 1 2.540(6) 2.773(8) 2.732(6) 2.887(8) 2.654(8) 2 2.511(10) 2.765(12) 2.728(11) 2.834(12) 2.635(15) 3 2.543(4) 2.772(5) 2.701(4) 2.829(4) 2.654(4) 4 2.524(12) 2.766(13) 2.696(11) 2.818(13) 2.690(13) 5@ 2.567(7) 2.751(8) 2.709(8) 2.809(8) 2.687(7) 2.777(8) 2.769(7) @Compound 5 crystallizes in a non-centrosymmetric space group (P21 ).
Consequently, unlike compounds 1-4, there is no crystallographic inversion center across b and c.
1:~
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Although preferred embodiments have been described herein in detail, it is understood by those skilled in the art that variations may be made thereto without departing from the scope of the invention as defined by the appended claims.

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Claims (52)

Claims:
1. A synthetic, supramolecular laminate class of organic compounds having a polymeric two dimensional flexible architecture comprising organic and metal-organic clay materials of first row transition metals, wherein the compounds comprise repeating asymmetric units which self assemble into laminated three-dimensional structures that are expandable with the reversible incorporation of a hydrophobic guest molecule within the compound.
2. The compound as claimed in claim 1, wherein said compound comprises ammonium salts of polycarboxylic acids.
3. The compound as claimed in claim 2, wherein said compound comprises primary ammonium salts of polycarboxylic acids.
4. The compound as claimed in claim 2, wherein said compound comprises secondary ammonium salts of polycarboxylic acids.
5. The compound as claimed in claim 3 or 4 wherein said polycarboxylic acid is a saturated or unsaturated organic aromatic acid having at least three carboxylic groups.
6. The compound as claimed in claim 5, wherein said polycarboxylic acid is selected from the group consisting of pyromellitic acid, trimesic acid, trimellitic acid and naphthalene carboxylic acid.
A synthetic supramolecular laminate compound of claim 1 comprising repeating asymmetric units having the formula: [[NR2H2]x[X)y]z wherein;
X is a polycarboxylic acid;

R is selected from the group consisting of; hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having from 1 to 5 phenyl rings, a benzyl group, a phenylethyl group, a phenyl butyl group, an alkylene group, an ethyl ether and an alcohol;
x and y are present in a ratio of 2:1; and z>0 wherein said compound is a hydrophobic clay compound.
8. The compound as claimed in claim 7, wherein said polycarboxylic acid is a saturated or unsaturated organic aromatic acid having at least three carboxylic groups.
9. A compound as claimed in claim 8 wherein the polycarboxylic acid is selected from the group consisting of pyromellitic acid, trimesic acid, trimellitic acid and naphthalene tricarboxylic acid.
10. The compound as claimed in claim 7, wherein said compound is selected from the group consisting of [N,N-dipropylammonium]2[HTMA], [N,N-dihexylammonium]2[HTMA], [N,N-dioctylammonium]2[HTMA], [N,N-didecylammonium]2[HTMA], [N,N-dibenzylammonium] and [N,N-dipropylammonium][HTMA].
11. The compound as claimed in claim 7, wherein said compound is selected from the group consisting of C328H372O58N16, C21H36N2O6, C33H60N2O6, C41H76N2O6, C49H92N2O6, C133H148N8O25 and C200H244N16O58.
12. The compound as claimed in claim 7, wherein said compound self-assembles into a laminated structure having intercalated guest molecules.
13. The compound as claimed in claim 12, wherein said guest molecules are intercalated via hydrogen bonding or three-dimensional aromatic stacking.
14. The compound as claimed in claim 13, wherein said guest molecules are selected from the group consisting of nitrobenzene, anisole, veratrole, 1,4-dimethoxybenzene, 1,3,5-trimethoxybenzene, m-xylene, mesitylene, p-nitroaniline, tetramethylene, pentamethylbenzene, hexamethylbenzene, dibenzylamine, naphthalene, 1-methylnaphthalene, pyrene, tetracyanoethylene, tetrathiafulvalene, ferrocene, drugs, food additives, water pollutants, air pollutants, explosives, fluorescent molecules, pheromones, phosphorescent molecules or nonlinear optic active molecules.
15. The compound as claimed in claim 13, wherein said compound has a crystal packing mode selected from the group consisting of corrugated sheets and guest, flat sheets with identical adjacent layers and guest, and flat sheets with alternating layers and guest.
16. A method for making a compound having the formula : [[NR2H2]x[X]y]z, wherein;
X is a polycarboxylic acid;
R is selected from the group consisting of; hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having from 1 to 5 phenyl rings, a benzyl group, a phenylethyl group, a phenyl butyl group, an alkylene group, an ethyl ether and an alcohol;
x and y are present in a ratio of 2:1; and z>0, the method comprising:
-reacting a solution of amine with a solution of polycarboxylic acid in a suitable solvent in a ratio of 2:1 by volume;
-evaporating the solvent from the admixed solutions to obtain crystals.
17. The method as claimed in claim 16, wherein the admixed solutions are refluxed prior to the evaporation of the solvent.
18. The method as claimed in claim 16 wherein said polycarboxylic acid is a saturated or unsaturated aromatic acid having at least three carboxylic groups.
19. The method as claimed in claim 18, wherein said polycarboxylic acid is selected from the group consisting of pyromellitic acid, trimesic acid, trimellitic acid and naphthalene carboxylic acid
20. The method as claimed in claim 16, wherein said amine is an ammonium compound.
21. The method as claimed in claim 16, wherein said solvent is selected from the group consisting of methyl alcohol, ethyl alcohol and water.
22. The compound as claimed in claim 1, wherein said compound comprises crystallized two dimensional open framework square grid polymers of metal-organic materials.
23. A supramolecular laminate of claim 1 having the formula:
[M(L)2(L')a X b]n wherein:
M is a metal ion;
L is a linear bifunctional ligand;
L' is a terminal ligand;
X is a counterion;
a is zero, 1 or 2;
b is equal to 1, 2 or 3; and n>0, wherein said supramolecular laminate has a flexible two-dimensional crystal structure that expands upon adsorption of a guest molecule and contracts upon desorption of said guest molecule.
24. The supramolecular laminate of claim 23, wherein M is a divalent or trivalent metal ion having an octahedral or square planar metal center.
25. The supramolecular laminate of claim 24, wherein said metal ion is selected from the group consisting of Co, Ni, Cu and Zn.
26. The supramolecular laminate of claim 23, wherein L is selected from the group consisting of 4, 4'-bi pyridine and bis(4-pyridyl)ethane.
27. The supramolecular laminate of claim 23, wherein L' is selected from the group consisting of water, ammonia and pyridine.
28. The supramolecular laminate of claim 23, wherein said counterion is selected from the group consisting of NO3, Cl, SO4, SiF6 and PF6.
29. The supramolecular laminate of claim 28, wherein said counterion may or may not be coordinated to said metal ion.
30. The supramolecular laminate of claim 23, wherein said compound crystallizes as an open framework square grid coordination polymer in the presence of guest molecules.
31. The supramolecular laminate of claim 23, wherein said compound has reversibly intercalated guest molecules.
32. The supramolecular laminate of claim 31, wherein said west molecules are organic molecules.
33. The supramolecular laminate of claim 32. wherein said guest molecules are selected from the group consisting of nitrobenzene, benzene, toluene, xylenes.
anisole, veratrole, napthalene, methylnapthalene, 1,2-dimethoxybenzene, pyrene and mixtures thereof.
34. The supramolecular laminate of claim 23, wherein said compound is selected from the group consisting of [Co(4,4'-bipyridine)2(NO3)2]n and [Ni(4,4'bipyridine)2(NO3)2]n, wherein n>O.
35. A method of making a metal a supramolecular laminate having the formula [M(L)2(L')a X b]n, wherein:
M is a metal ion;
L is a linear bifunctional ligand;
L' is a terminal ligand;
X is a counterion;
a is zero, 1 or 2;
b is equal to 1, 2 or 3; and n>0, said method comprising:
-forming a reacting interface between a metal organic solution and a ligand solution, wherein after a period of time the reaction product forms in the interface and comes out of solution as crystals.
36. The method as claimed in claim 35, wherein said method further comprises the step of separating the formed crystals from solution.
37. The method as claimed in claim 35, wherein said metal organic solution is Co(NO3)2-6H2O in methyl alcohol.
38. The method as claimed in claim 35, wherein said metal organic solution is Ni(NO3)2-6H2O in methyl alcohol,
39. The method as claimed in claim 35, wherein said ligand solution is 4,4'-bipyridine in a solvent selected from the group consisting of benzene, chlorobenzene and naphthalene.
40. The use of the compound of claim 1, 7 or 23, as an adsorbent or desorbent of organic compounds.
41. The use of the compound of claim 1, 7 or 23, as a catalyst in a catalysis reaction.
42. The use of the compound of claim 1, 7 or 23, as a liquid crystal.
43. The use of the compound of claim 1, 7 or 23, as an nonlinear optic active material.
44. The use of the compound of claim 1, 7 or 23, as a chemical sensor.
45. The use of the compound of claim 1, 7 or 23, for the slow release of drugs in vitro and in vivo.
46. The use of the compound of claim 1, 7 or 23, for crop remediation.
47. The use of the compound of claim 1, 7 or 23, for environmental remediation of gases and liquids.
48. The use of the compound of claim 1, 7 or 23, as a stabilizer or binder for explosives and fuels.
49. The use of the compound of claim 1, 7 or 23, as a binder for food additives.
50. The use of the compound of claim 1, 7 or 23, as a precursor for a covalent polymer.
51. The use of the compound of claim 1, 7 or 23, for gas separations.
52. The compound of claim 1, 7 or 23, wherein a hydrophobic guest molecule is incorporated within the compound, said guest molecule being selected from the group consisting of nitrobenzene, benzene, toluene, xylene, anisole, veratrole, naphthalene, methylnaphthalene, 1,2-dimethoxybenzene, pyrene and mixture thereof.
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