ELECTRO-POLARIZABLE COMPLEX COMPOUND AND CAPACITOR
20170372842 · 2017-12-28
Inventors
- Pavel Ivan Lazarev (Menlo Park, CA, US)
- Paul T. Furuta (Sunnyvale, CA, US)
- Barry K. Sharp (Redwood City, CA, US)
Cpc classification
International classification
C07F5/00
CHEMISTRY; METALLURGY
Abstract
The present disclosure provides an electro-polarizable complex compound having the following general formula:
[M.sup.4+(L).sub.m].sup.xK.sub.n, (I)
where complexing agent M is a four-valence metal; ligand L comprises one or more heteroatomic fragments comprising one or more neutral or anionic metal-coordinating heteroatoms and one or more electrically resistive fragments, m represents the number of ligands; x represents the oxidative state of the metal-ligand complex; K is a counter-ion or zwitterionic polymers which provides an electro-neutrality of the complex compound, n represents the number of counter-ions. The metal-coordinating heteroatoms form a first coordination sphere, and the number of heteroatoms in this first coordination sphere does not exceed 12.
Claims
1. An electro-polarizable complex compound having the following general formula:
[M.sup.4+(L).sub.m].sub.xK.sub.n, (I) where M is a four-valence metal complexing agent, ligand L is a first ligand having one or more heteroatomic fragments comprising one or more neutral or anionic metal-coordinating heteroatoms and one or more electrically resistive fragments, m represents the number of ligands, x represents the oxidative state of the metal-ligand complex, K is a counter-ion or zwitterionic polymer which provides an electro-neutrality of the complex compound, n represents the number of counter-ions or zwitterionic polymers, wherein said one or more neutral or anionic metal-coordinating heteroatoms form a first coordination sphere, and the number of heteroatoms in this first coordination sphere does not exceed 12.
2. The complex compound according to claim 1, wherein the four-valence metal is selected from the set comprising cerium, thorium, lead, titanium, zirconium, tin, palladium, platinum, osmium, iridium, germanium, manganese, and hafnium.
3. The complex compound according to claim 1, wherein the electrically resistive fragment provides resistivity to electric current and comprises hydrocarbon (saturated and/or unsaturated), fluorocarbon, siloxane, and/or polyethylene glycol as linear or branched chains.
4. The complex compound according to claim 1, wherein the electrically resistive fragments are cross-linked.
5. The complex compound according to claim 1, wherein the electrically resistive fragments are fluorinated.
6. The complex compound according to claim 1, wherein K is N.sup.+R.sub.4, where R is hydrogen (H), Fluorine (F) or an alkyl group.
7. The complex compound according to claim 1, wherein the counter-ion is selected from one or multiple ionic groups from the class of ionic compounds that are used in ionic liquids connected directly or via a connecting group to at least one ligand.
8. The complex compound according to claim 7, wherein at least one ionic group is selected from the list comprising [NR.sub.4].sup.+, [PR.sub.4].sup.+ as cation and [—CO.sub.2].sup.−, [—SO.sub.3].sup.−, [—SR.sub.5].sup.−, [—PO.sub.3R].sup.−, [—PR.sub.5].sup.− as anion, wherein R is selected from the set comprising hydrogen (H), alkyl, and fluorine.
9. The complex compound according to claim 7, wherein at least one connecting group is selected from the set comprising CH.sub.2, CF.sub.2, SiR.sub.2O, CH.sub.2CH.sub.2O, wherein R is selected from the hydrogen (H), alkyl, and fluorine.
10. The complex compound according to claim 7, wherein at least one connecting group is selected from structures 1-9, where X is hydrogen (H) or an alkyl group: ##STR00049##
11. The electro-polarizable compound according to claim 1, wherein the at least one connecting group is selected from structures 11 to 16: ##STR00050##
12. The complex compound according to claim 1, wherein the counter-ion is selected from one or multiple ionic groups from the class of ionic compounds that are zwitterionic polymers.
13. The complex compound according to claim 12, wherein the zwitterionic polymer is N-Dodecyl-N,N-(dimethylammonio)butyrate having the following structural formula: ##STR00051## wherein two atoms of oxygen of carboxyl group take part in formation of the first coordination sphere and the cation N.sup.+ serves as a counter-ion.
14. The complex compound according to claim 1, having the following general formula:
Ce.sup.4+(Ste.sup.−).sub.4+m[N(but).sup.+.sub.4].sub.m, (II) where m≧2; Ste is anion of stearic acid comprising atoms of oxygen as heteroatoms and an electrically resistive alkyl chain as the resistive fragment, and N(but).sup.+.sub.4 is a cation of tetrabutyl ammonium.
15. The complex compound according to claim 1, wherein the ligand L has the following general formula:
(R.sub.1).sub.k-Core-(R.sub.2).sub.p, (III) where Core is an aromatic polycyclic conjugated anisotropic molecule, R.sub.1 is an electrically resistive substituent that includes saturated and/or unsaturated hydrocarbon, fluorocarbon, siloxane, and/or polyethylene glycol as linear or branched chains, R.sub.2 is a substitute comprising the one or more neutral or anionic metal-coordinating heteroatoms, k=1, 2, 3, and 4, p=1, 2, 3, 4, 5, 6, 7, and 8, wherein said aromatic polycyclic conjugated molecule (Core) forms supramolecules in the suitable solvent.
16. The complex compound according to claim 15, wherein the aromatic polycyclic conjugated molecule is a rylene fragment, R.sub.1 is an electrically resistive substituent that provides resistivity to electric current and comprises hydrocarbon (saturated and/or unsaturated), fluorocarbon, siloxane, and/or polyethylene glycol as linear or branched chains located in terminal/apex positions, R.sub.2 is a heteroatom functional group with one or more neutral or anionic metal-coordinating heteroatoms located in lateral or bay positions.
17. The complex compound according to claim 15, wherein the aromatic polycyclic conjugated molecule is a rylene fragment, R.sub.1 is an electrically resistive substituent that includes saturated and/or unsaturated hydrocarbon, fluorocarbon, siloxane, and/or polyethylene glycol as linear or branched chains located in terminal/apex positions, R.sub.2 is a heteroatom functional group with one or more neutral or anionic metal-coordinating heteroatom located in terminal or apex positions.
18. The complex compound according to any of claim 16 or 17, wherein the rylene fragments are selected from structures 17 to 37. ##STR00052## ##STR00053## ##STR00054##
19. The complex compound according to claim 15, wherein the aromatic polycyclic conjugated molecule (Core) is tetrapirolic macro-cyclic fragment, R.sub.1 is an electrically resistive substitute that provides resistivity to electric current and comprises hydrocarbon (saturated and/or unsaturated), fluorocarbon, siloxane, and/or polyethylene glycol as linear or branched chains, R.sub.2 is a heteroatom functional group with one or more neutral or anionic metal-coordinating heteroatom.
20. The complex compound according to claim 19, wherein the tetrapirolic macro-cyclic fragments have a general structural formula from the group of structures 38-44, where M denotes an atom of four-valence metal: ##STR00055## ##STR00056##
21. The complex compound according to claim 15, wherein the aromatic polycyclic conjugated molecule (Core) is phthalocyonine, R.sub.1 is an alkyl chain, R.sub.2 is anion of carboxylic group as a heteroatomic fragment containing the one or more neutral or anionic metal-coordinating heteroatoms.
22. The complex compound according to claim 21 has the following structure formula: ##STR00057##
23. A solution comprising an organic solvent and at least one electro-polarizable complex compound according to claim 1.
24. The solution according to claim 23, wherein the organic solvent is selected from the list comprising ketones, carboxylic acids, hydrocarbons, cyclohydrocarbons, chlorohydrocarbons, alcohols, ethers, esters, and any combination thereof.
25. The solution according to claim 23, wherein the organic solvent is selected from the list comprising acetone, xylene, toluene, ethanol, methylcyclohexane, ethyl acetate, diethyl ether, octane, chloroform, methylenechloride, dichloroethane, trichloroethene, tetrachloroethene, carbon tetrachloride, 1,4-dioxane, tetrahydrofuran, pyridine, triethylamine, nitromethane, acetonitrile, dimethylformamide, dimethyl sulfoxide, and any combination thereof.
26. The solution according to claim 23, wherein the solution is a lyotropic liquid crystal solution.
27. A crystal meta-dielectric layer comprising a mixture of the electro-polarizable complex compounds according to claim 1.
28. The crystal meta-dielectric layer of claim 27, wherein the four-valence metals are placed into a resistive dielectric envelope formed by the one or more electrically resistive fragments wherein atoms of the four-valence metals, the organic molecules of the ligands, or the one or more neutral or anionic metal-coordinating heteroatoms have electronic or ionic type of polarizability.
29. The crystal meta-dielectric layer of claim 27, wherein the layer's relative permittivity is greater than or equal to 1000.
30. The crystal meta-dielectric layer of claim 27, wherein the layer's resistivity is greater than or equal to 10.sup.13 ohm-cm.
31. A meta-capacitor comprising two metal electrodes positioned parallel to each other and which are rolled or flat and planar and a meta-dielectric layer between the two electrodes, wherein the meta-dielectric layer comprises the electro-polarizable complex compounds according to claim 1.
32. The meta-capacitor of claim 31, wherein polarizable atoms of the four-valence metals are placed into a resistive dielectric envelope formed by the one or more electrically resistive fragments where atoms of the four-valence metals, organic molecules of ligands, or the heteroatoms have electronic or ionic type of polarizability.
33. The complex compound of claim 1, the complex compound having an at least one second ligand, the second ligand having different structure than the first ligand and wherein the second ligand is part of the first coordination sphere.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] A more complete assessment of the present invention and its advantages will be readily achieved as the same becomes better understood by reference to the following detailed description, considered in connection with the accompanying drawings and detailed specification, all of which forms a part of the disclosure. Embodiments of the invention are illustrated, by way of example only, in the following Figures, of which:
[0029]
[0030]
[0031]
[0032]
[0033]
[0034]
DETAILED DESCRIPTION
[0035] While various embodiments of the invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions may occur to those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed.
[0036] Although the following detailed description contains many specific details for the purposes of illustration, anyone of ordinary skill in the art will appreciate that many variations and alterations to the following details are within the scope of the invention. Accordingly, the exemplary embodiments of the invention described below are set forth without any loss of generality to, and without imposing limitations upon, the claimed invention.
[0037] In the following detailed description, reference is made to the accompanying drawings, which form a part hereof, and in which is shown by way of illustration specific non-limiting embodiments in which the invention may be practiced. In this regard, directional terminology, such as “top,” “bottom,” “front,” “back,” “first,” “second,” etc., is used with reference to the orientation of the figure(s) being described. Because components of embodiments of the present invention can be positioned in a number of different orientations, the directional terminology is used for purposes of illustration and is in no way limiting. It is to be understood that other embodiments may be utilized and structural or logical changes may be made without departing from the scope of the present invention. The following detailed description, therefore, is not to be taken in a limiting sense, and the scope of the present invention is defined by the appended claims.
[0038] Additionally, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a thickness range of about 1 nm to about 200 nm should be interpreted to include not only the explicitly recited limits of about 1 nm and about 200 nm, but also to include individual sizes such as but not limited to 2 nm, 3 nm, 4 nm, and sub-ranges such as 10 nm to 50 nm, 20 nm to 100 nm, etc. that are within the recited limits.
[0039] The present disclosure provides an electro-polarizable complex compound as disclosed above. Essential distinctive feature of the present invention is existence of the electrically resistive fragments as ligands. These fragments create a resistive envelop around the complexing agent M and the first coordination sphere. The resistive envelop isolates the molecules of disclosed electro-polarizable complex compound from each other. In one embodiment of the electro-polarizable complex compound, the four-valence metal is selected from the set comprising cerium, thorium, lead, titanium, zirconium, tin, palladium, platinum, osmium, iridium, germanium, manganese, and hafnium. In another embodiment of the electro-polarizable complex compound, the electrically resistive fragment provides resistivity to electric current and comprises hydrocarbon (saturated and/or unsaturated), fluorocarbon, siloxane, and/or polyethylene glycol as linear or branched chains. In yet another embodiment of the present disclosure, the electrically resistive fragments are cross-linked. In still another embodiment of the present disclosure, the electrically resistive fragments are fluorinated. In one embodiment of the present disclosure, the counter-ion K is R.sub.4, where R can be Fluorine (F) or an alkyl group. By way of example and not by way of limitation, the counter-ion or zwitterionic polymer K may be N.sup.+(C.sub.4H.sub.9).sub.4 or NH.sub.4.sup.+. In another embodiment of the disclosed complex compound, the counter-ion is selected from one or multiple ionic groups from the class of ionic compounds that are used in ionic liquids are connected directly or via a connecting group to at least one ligand. In yet another embodiment of the disclosed complex compound, the at least one ionic group is selected from the list comprising [NR.sub.4].sup.+, [PR.sub.4].sup.+ as cation and [—CO.sub.2].sup.−, [—SO.sub.3].sup.−, [—SR.sub.5].sup.−, [—PO.sub.3R].sup.−, [—PR.sub.5].sup.− as anion, wherein R is selected from the set comprising H, alkyl, and fluorine. In still another embodiment of the disclosed complex compound, the at least one connecting group is selected from the set comprising CH.sub.2, CF.sub.2, SiR.sub.2O, CH.sub.2CH.sub.2O, wherein R is selected from the set comprising H, alkyl, and fluorine. In one embodiment of the present disclosure, at least one connecting group is selected from the list comprising the following structures 1-9 as shown in Table 1.
TABLE-US-00001 TABLE 1 Examples of the connecting group where X can be hydrogen (H) or an alkyl group
[0040] In another embodiment of the present disclosure, at least one connecting group is selected from the list comprising the following structures 11-16 as shown in Table 2.
TABLE-US-00002 TABLE 2 Examples of the connecting group
In one embodiment of the complex compound, the counter-ion is selected from one or multiple ionic groups from the class of ionic compounds that are zwitterionic polymers. In another embodiment of the complex compound, the zwitterionic polymer is N-Dodecyl-N,N-(dimethylammonio)butyrate having the following structural formula:
##STR00015##
[0041] wherein two atoms of oxygen of carboxyl group take part in formation of the first coordination sphere and the cation N.sup.+ serves as the counter-ion.
[0042] In still another embodiment of the present disclosure, the complex compound has the following general formula:
Ce.sup.4+(Ste.sup.−).sub.4+m[N(but).sup.+.sub.4].sub.m, (II)
where m≧2; Ste is anion of stearic acid comprising atoms of oxygen as heteroatoms and an electrically resistive alkyl chain as the resistive fragment, a counter-ion N(but).sup.+.sub.4 is cation of tetrabutyl ammonium.
[0043]
[0044]
[0045] The molecular structure shown in
[0046] In yet another embodiment of the present disclosure, the ligand L has the following general formula:
(R.sub.1).sub.k-Core-(R.sub.2).sub.p, (III)
where Core is an aromatic polycyclic conjugated anisotropic molecule, R.sub.1 is an electrically resistive substituent that provides resistivity to electric current and comprises hydrocarbon (saturated and/or unsaturated), fluorocarbon, siloxane, and/or polyethylene glycol as linear or branched chains, R.sub.2 is a substitute comprising at least one metal-coordinating heteroatom (neutral or anionic), k=1, 2, 3, and 4, p=1, 2, 3, 4, 5, 6, 7, and 8. Said aromatic polycyclic conjugated molecule (Core) forms supramolecules in the suitable solvent. In still another embodiment of the present disclosure in the general formula (III) the aromatic polycyclic conjugated molecule is a rylene fragment, R.sub.1 is an electrically resistive substituent that provides resistivity to electric current and comprises hydrocarbon (saturated and/or unsaturated), fluorocarbon, siloxane, and/or polyethylene glycol as linear or branched chains located in terminal/apex positions, R.sub.2 is a heteroatom functional group with at least one metal-coordinating heteroatom (neutral or anionic) located in lateral/bay positions. For an explanation of the used terms the structural formula of organic compound is shown below in which the substitutes R′ are located in terminal/apex positions and substitutes R″ are located in lateral/bay positions:
##STR00016##
In yet another embodiment of the present disclosure in the general formula (III) the aromatic polycyclic conjugated molecule is a rylene fragment, R.sub.1 is an electrically resistive substituent that provides resistivity to electric current and comprises hydrocarbon (saturated and/or unsaturated), fluorocarbon, siloxane, and/or polyethylene glycol as linear or branched chains located in terminal/apex positions, R.sub.2 is a heteroatom functional group with at least one metal-coordinating heteroatom (neutral or anionic) located in terminal/apex positions. In one embodiment of the present disclosure, the rylene fragments in the general formula (III) are selected from the structures 17 to 37 as shown in Table 3.
TABLE-US-00003 TABLE 3 Examples of the rylene fragments
[0047] One example of an embodiment of the present invention, molecules of nitrate of perylene comprising two nitro-groups (—NO.sub.2) located in lateral/bay positions and electrically resistive substituents (for example, C.sub.18H.sub.37) located in terminal/apex positions are used. These molecules form molecular stacks due to pi-pi interaction. These stacks will be coordinated to the Ce ion in planes orthogonal to one another. In this embodiment also ammonium cerium (IV) nitrate (NH.sub.4.sup.+).sub.2Ce(NO.sub.3).sub.6 in which anion [Ce(NO.sub.3).sub.6)].sup.2− is neutralized by an ammonium cation NH.sub.4.sup.+ is used. Nitro-groups of perylene replace four NO.sub.3.sup.−-groups. The complex compound shown in
[0048] In another embodiment of the present disclosure, the aromatic polycyclic conjugated molecule (Core) in the general formula (III) is tetrapirolic macro-cyclic fragment, R.sub.1 is an electrically resistive substitute that provides resistivity to electric current and comprises hydrocarbon (saturated and/or unsaturated), fluorocarbon, siloxane, and/or polyethylene glycol as linear or branched chains, R.sub.2 is a heteroatom functional group with at least one metal-coordinating heteroatom (neutral or anionic). In yet another embodiment of the present disclosure, the tetrapirolic macro-cyclic fragments have a general structural formula from the group comprising structures 38-44 as shown in Table 4, where M denotes an atom of four-valence metal.
TABLE-US-00004 TABLE 4 Examples of the tetrapirolic macro-cyclic fragments
In still another embodiment of the present disclosure, the aromatic polycyclic conjugated molecule (Core) is phthalocyonine, R.sub.1 is an alkyl chain, R.sub.2 is anion of carboxylic group as the heteroatomic fragment. In yet another embodiment of the present disclosure, the complex compound has the following structure formula:
##STR00045##
[0049] Molecules of oxygen on carboxyl groups take part in formation of the first coordination sphere round the complexing agent M. The electrically resistive fragments ((C.sub.1-C.sub.20)alkyl) create a dielectric cover round the complexing agent M and the first coordination sphere.
[0050] The present disclosure provides the solution comprising the electro-polarizable complex compound as disclosed above. In one embodiment of the present disclosure, the disclosed solution comprises the organic solvent selected from the list comprising ketones, carboxylic acids, hydrocarbons, cyclohydrocarbons, chlorohydrocarbons, alcohols, ethers, esters, and any combination thereof. In another embodiment of the present disclosure, the organic solvent is selected from the list comprising acetone, xylene, toluene, ethanol, methylcyclohexane, ethyl acetate, diethyl ether, octane, chloroform, methylene chloride, dichloroethane, trichloroethene, tetrachloroethene, carbon tetrachloride, 1,4-dioxane, tetrahydrofuran, pyridine, triethylamine, nitromethane, acetonitrile, dimethylformamide, dimethyl sulfoxide, and any combination thereof. In yet another embodiment of the present disclosure, the solution is a lyotropic liquid crystal solution.
[0051] The present disclosure provides the crystal meta-dielectric layer as disclosed above. In one embodiment of the present disclosure, the layer's relative permittivity is greater than or equal to 1000. In another embodiment of the crystal meta-dielectric layer, the real part of the relative permittivity (∈′) of the layer comprises first-order (∈.sup.(1)), second-order (∈.sup.(2)) and third-order (∈.sup.(3)) permittivity according to follow formula:
∈′=∈.sup.(1)+∈.sup.(2).Math.V.sub.0/d+∈.sup.(3).Math.(V.sub.0/d).sup.2,
where V.sub.0 is the DC-voltage which is applied to the crystal meta-dielectric layer, d is the layer thickness. In yet another embodiment of the present disclosure, the layer's resistivity is greater than or equal to 10.sup.13 ohm-cm.
[0052] The present disclosure provides the meta-capacitor comprising two metal electrodes positioned parallel to each other and which can be rolled or flat and planar and meta-dielectric layer between this electrodes. The layer comprises the electro-polarizable complex compounds as disclosed above. The polarizable atoms of the four-valence metals are placed into the resistive dielectric envelope formed by resistive fragments of the electrically resistive substituent where atoms of the four-valence metals, organic molecules of ligands, or heteroatoms have electronic or ionic type of polarizability.
[0053] The meta-capacitor comprises a first electrode 11, a second electrode 12, and a meta-dielectric layer 13 disposed between said first and second electrodes as shown in
[0054] The electrodes 11, 12 may be flat and planar and positioned parallel to each other. Alternatively, the electrodes may be planar and parallel, but not necessarily flat, they may be coiled, rolled, bent, folded, or otherwise shaped to reduce the overall form factor of the capacitor. It is also possible for the electrodes to be non-flat, non-planar, or non-parallel or some combination of two or more of these. By way of example and not by way of limitation, a spacing d between the electrodes 11, 12 may range from about 100 nm to about 10,000 μm. The maximum voltage V.sub.bd between the electrodes 11, 12 is approximately the product of the breakdown field E.sub.bd and the electrode spacing d. If E.sub.bd=0.1 V/nm and the spacing d between the electrodes 11 and 12 is 10,000 microns (100,000 nm), the maximum voltage V.sub.bd would be 100,000 volts.
[0055] The electrodes 11, 12 may have the same shape as each other, the same dimensions, and the same area A. By way of example, and not by way of limitation, the area A of each electrode 11, 12 may range from about 0.01 m.sup.2 to about 1000 m.sup.2. By way of example and not by way of limitation, for rolled capacitors, electrodes up to, e.g., 1000 m long and 1 m wide.
[0056] These ranges are non-limiting. Other ranges of the electrode spacing d and area A are within the scope of the aspects of the present disclosure.
[0057] If the spacing d is small compared to the characteristic linear dimensions of electrodes (e.g., length and/or width), the capacitance C of the capacitor may be approximated by the formula:
C=∈∈.sub.0A/d, (IV)
where ∈.sub.o is the permittivity of free space (8.85×10.sup.−12 Coulombs.sup.2/(Newton.Math.meter.sup.2)) and E is the dielectric constant of the dielectric layer. The energy storage capacity U of the capacitor may be approximated as:
U=½∈∈.sub.oAE.sub.bd.sup.2 (V)
[0058] The energy storage capacity U is determined by the dielectric constant ∈, the area A, and the breakdown field E.sub.bd. By appropriate engineering, a capacitor or capacitor bank may be designed to have any desired energy storage capacity U. By way of example, and not by way of limitation, given the above ranges for the dielectric constant ∈, electrode area A, and breakdown field E.sub.bd a capacitor in accordance with aspects of the present disclosure may have an energy storage capacity U ranging from about 500 Joules to about 2.Math.10.sup.16 Joules.
[0059] For a dielectric constant E ranging, e.g., from about 100 to about 1,000,000 and constant breakdown field E.sub.bd between, e.g., about 0.1 and 0.5 V/nm, a capacitor of the type described herein may have a specific energy capacity per unit mass ranging from about 10 W.Math.h/kg up to about 100,000 W.Math.h/kg, though implementations are not so limited.
[0060] The present disclosure include meta-capacitors that are coiled, e.g., as depicted in
[0061] Certain aspects of the present disclosure will now be described more fully hereinafter with reference to the following examples, in which preferred embodiments of the present invention are shown. This invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
[0062] This Example describes synthesis of the disclosed organic compound according following structural scheme:
##STR00046##
[0063] To obtain [Ce.sup.4+(Ste.sup.−).sub.4].sub.x, 0.50 g of Ce(OH).sub.4 was added 1.5 g of acetic acid and 2.05 g of stearic acid. The mixture was heated to 100° C. for 3 hours in an apparatus fitted with dry molecular sieves to absorb the water of condensation. The reaction was then placed under vacuum while heating to remove the rest of the condensed water and acetic acid, affording 2.38 g of yellow solid [Ce.sup.4+(Ste.sup.−).sub.4].sub.x.
[0064] To obtain Ce.sup.4+(Ste.sup.−).sub.4+m[N(but).sup.+.sub.4].sub.m, 1.00 g of the above [Ce.sup.4+(Ste.sup.−).sub.4].sub.x was added 5 mL of toluene, 0.447 g of stearic acid, and 2.147 g of a 20% solution of TBA-OMe in methanol. The suspension was heated to 50° C. for 30 minutes, and then the residual solvents were removed under reduced pressure at 50° C. until there was no more weight loss, yielding 1.83 g Ce.sup.4+(Ste.sup.−).sub.4+m[N(but).sup.+.sub.4].sub.m.
Example 2
[0065] This Example describes synthesis of a disclosed organic compound according following structural scheme:
##STR00047##
[0066] Perylene bisimide (1, 2.7 g, 2.4 mmol) was dissolved in 20 mL of THF. Then, Cerric ammonium nitrate (CAN, 0.219 g, 0.4 mmol) was dissolved in a minimum amount of MeOH and added to the THF solution. The mixture was stirred overnight at 40° C., and filtered to give 2.7 g of Ce.sup.4+(NO.sub.3).sub.4(1)
Example 3
[0067] This Example describes synthesis of a disclosed organic compound according following structural scheme:
##STR00048##
[0068] Cerium(IV) stearate (synthesis shown in Example 1) (CeSt.sub.4, 1 equiv.) and 2 (1 equiv.) were dissolved in CHCl.sub.3.
[0069] While the present disclosure includes a complete description of the preferred embodiment of the present invention, it is possible to use various alternatives, modifications and equivalents. Therefore, the scope of the present invention should be determined not with reference to the above description but should, instead, be determined with reference to the appended claims, along with their full scope of equivalents. Any feature described herein, whether preferred or not, may be combined with any other feature described herein, whether preferred or not. In the claims that follow, the indefinite article “A”, or “An” refers to a quantity of one or more of the item following the article, except where expressly stated otherwise. As used herein, in a listing of elements in the alternative, the word “or” is used in the logical inclusive sense, e.g., “X or Y” covers X alone, Y alone, or both X and Y together, except where expressly stated otherwise. Two or more elements listed as alternatives may be combined together. The appended claims are not to be interpreted as including means-plus-function limitations, unless such a limitation is explicitly recited in a given claim using the phrase “means for.”