ELECTRO-POLARIZABLE COMPOUND AND CAPACITOR

Abstract

An electro-polarizable compound has the following general formula:

##STR00001## where Core1 is an aromatic polycyclic conjugated molecule having two-dimensional flat form and self-assembling by pi-pi stacking in a column-like supramolecule, which is tetrapirolic macro-cyclic fragment, R1 is an dopant group connected to Core1, m is number of R1 which is equal to 1, 2, 3 or 4, R2 is a substituent comprising one or more ionic groups, p is number of R2 which is equal to 0, 1, 2, 3 or 4. The fragment marked NLE containing the Core1 with at least one R1 has a nonlinear effect of polarization. Core2 is an electro-conductive oligomer self-assembling by pi-pi stacking in a column-like supramolecule, n is number of Core2 which is equal to 2, or 4, R3 is a substituent comprising one or more ionic groups, s is number of R3 which is equal to 0, 1, 2, 3 or 4. R4 is a non-polar resistive substituent, k is a number of R4 which is equal to 0, 1, 2, 3, 4, 5, 6, 7 or 8.

Claims

1. An electro-polarizable compound having the following general formula (I): ##STR00160## where Core1 is an aromatic polycyclic conjugated molecule having two-dimensional flat form and self-assembling by pi-pi stacking in a column-like supramolecule, R1 is an dopant group connected to the aromatic polycyclic conjugated molecule (Core1), m is number of dopant groups R1 which is equal to 1, 2, 3 or 4, R2 is a substituent comprising one or more ionic groups from a class of ionic compounds that are used in ionic liquids connected to the aromatic polycyclic conjugated molecule (Core1) directly or via a connecting group, p is number of ionic groups R2 which is equal to 0, 1, 2, 3 or 4; wherein the fragment marked NLE containing the Core1 with at least one dopant group R1 has a nonlinear effect of polarization, wherein Core2 is an electro-conductive oligomer self-assembling by pi-pi stacking in a column-like supramolecule, n is number of the electro-conductive oligomers which is equal to 0, 2, or 4, R3 is a substituent comprising one or more ionic groups from a class of ionic compounds that are used in ionic liquids connected to the electro-conductive oligomer (Core2) directly or via a connecting group, s is number of the ionic groups R3 which is equal to 0, 1, 2, 3 or 4; wherein R4 is a resistive substituent providing solubility of the organic compound in a solvent and electrically insulating the column-like supramolecules from each other, k is a number of substituents R4 which is equal to 0, 1, 2, 3, 4, 5, 6, 7 or 8; wherein the aromatic polycyclic conjugated molecule (Core1) comprises rylene fragments.

2. The composite organic compound of claim 1, wherein the rylene fragments are selected from structures 1 to 12: TABLE-US-00008 1 2 3 4 5 6 7 8 9 10 11 12

3. The electro-polarizable compound according to claim 1, wherein the dopant group (R1) is selected from nucleophilic groups (donors) and electrophilic groups (acceptors).

4. The electro-polarizable compound according to claim 3, wherein the electrophilic groups (acceptors) are selected from NO.sub.2, NH.sub.3.sup.+ and NR.sub.3.sup.+ (quaternary nitrogen salts), counterion Cl.sup. or Br.sup., CHO (aldehyde), CRO (keto group), SO.sub.3H (sulfonic acids), SO.sub.3R (sulfonates), SO.sub.2NH.sub.2 (sulfonamides), COOH (carboxylic acid), COOR (esters, from carboxylic acid side), COCl (carboxylic acid chlorides), CONH.sub.2 (amides, from carboxylic acid side), CF.sub.3, CCl.sub.3, CN, wherein R is radical selected from the list comprising alkyl (methyl, ethyl, isopropyl, tert-butyl, neopentyl, cyclohexyl etc.), allyl (CH.sub.2CHCH.sub.2), benzyl (CH.sub.2C.sub.6H.sub.5) groups, phenyl (+substituted phenyl) and other aryl (aromatic) groups; and wherein the nucleophilic groups (donors) are selected from O.sup. (phenoxides, like ONa or OK), NH.sub.2, NHR, NR.sub.2, OH, OR (ethers), NHCOR (amides, from amine side), OCOR (esters, from alcohol side), alkyls, C.sub.6H.sub.5, vinyls, wherein R is radical selected from the list comprising alkyl (methyl, ethyl, isopropyl, tert-butyl, neopentyl, cyclohexyl etc.), allyl (CH2-CHCH2), benzyl (CH2C6H5) groups, phenyl (+substituted phenyl) and other aryl (aromatic) groups.

5. The electro-polarizable compound according to claim 1, wherein at least one ionic group R2 or R3 is independently 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 list comprising H, alkyl, and fluorine.

6. The electro-polarizable compound according to claim 1, wherein the at least one connecting group is selected from the list comprising the following structures: 29-45, where W is hydrogen (H) or an alkyl group: TABLE-US-00009 O 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

7. The electro-polarizable compound according to claim 1, wherein the at least one connecting group is selected from the group of CH.sub.2, CF.sub.2, SiR.sub.2O, CH.sub.2CH.sub.2O, wherein R is selected from the list comprising H, alkyl, and fluorine.

8. The electro-polarizable compound according to claim 1, wherein the resistive substituent R4 is selected from the group of alkyl, aryl, substituted alkyl, substituted aryl, fluorinated alkyl, chlorinated alkyl, branched and complex alkyl, branched and complex fluorinated alkyl, branched and complex chlorinated alkyl groups, and any combination thereof, and wherein the alkyl group is selected from methyl, ethyl, propyl, n-butyl, iso-butyl and tert-butyl groups, and the aryl group is selected from phenyl, benzyl and naphthyl groups or siloxane, and/or polyethyleneglycol as linear or branched chains.

9. The electro-polarizable compound according to claim 1, wherein the resistive substituent R4 is C.sub.XQ.sub.2X+1, where X1 and Q is hydrogen (H), fluorine (F), or chlorine (Cl).

10. The electro-polarizable compound of claim 1, wherein the aromatic polycyclic conjugated molecule (Core1) and the dopant groups (R1) form a non-centrosymmetric molecular structure.

11. The electro-polarizable compound of claim 1, wherein the aromatic polycyclic conjugated molecule (Core1), the dopant groups (R1) and the resistive substituents (R4) form a non-centrosymmetric molecular structure.

12. An electro-polarizable compound of claim 1, wherein a fragment comprising the aromatic polycyclic conjugated molecule (Core1), dopant groups (R1) and resistive substituents providing solubility of the organic compound in a solvent and electrically insulating the column-like supramolecules from each other (R4) is selected from structures 46 to 97: TABLE-US-00010 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97

13. A solution comprising an organic solvent and at least one type of electro-polarizable compound according to claim 1.

14. The solution according to claim 13, comprising a mixture of different electro-polarizable compounds.

15. The solution according to claim 13, wherein the organic solvent is selected from the list consisting of ketones, carboxylic acids, hydrocarbons, cyclic hydrocarbons, chlorohydrocarbons, alcohols, ethers, esters, 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.

16. The solution according claim 13, wherein the solution is a lyotropic liquid crystal solution.

17. A crystal metadielectric layer comprising a mixture of the electro-polarizable compounds according to claim 1, wherein the nonlinearly polarizable fragments comprising an aromatic polycyclic conjugated molecule with at least one dopant group, the electro-conductive oligomers and the ionic groups which have electronic and/or ionic type of polarizability are placed into the resistive dielectric envelope formed by resistive substituents providing solubility of the organic compound in a solvent and electrically insulating the column-like supramolecules from each other.

18. The crystal metadielectric layer according to claim 17, wherein the column-like supramolecules are formed by the electro-polarizable compounds comprising rylene fragments of different length.

19. The crystal metadielectric layer according to claim 17, wherein the layer's relative permittivity is greater than or equal to 1000 and the layer's resistivity is greater than or equal to 10.sup.13 ohm/cm.

20. A meta-capacitor comprising two metal electrodes positioned parallel to each other and which can be rolled or flat and planar and metadielectric layer between this electrodes, wherein the layer comprises the electro-polarizable compounds according to any claim 1, wherein the nonlinearly polarizable fragments comprising an aromatic polycyclic conjugated molecule with at least one dopant group, the electro-conductive oligomers and the ionic groups which have electronic and/or ionic type of polarizability are placed into the resistive dielectric envelope formed by resistive substituents providing solubility of the organic compound in a solvent and electrically insulating the column-like supramolecules from each other.

Description

BRIEF DESCRIPTION OF THE DRAWING

[0027] FIG. 1A schematically shows a capacitor with flat and planar electrodes in accordance with an aspect of the present disclosure.

[0028] FIG. 1B schematically shows a capacitor with rolled (circular) electrodes in accordance with another aspect of the present disclosure.

DETAILED DESCRIPTION

[0029] 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.

[0030] The present disclosure provides an electro-polarizable compound. Existence of the electrophilic groups (acceptors) and the nucleophilic groups (donors) in the aromatic polycyclic conjugated molecule (Core1) promotes increase of electronic polarizability of these molecules. Under the influence of external electric field electrons are displaced from the nucleophilic groups (donors) to the electrophilic groups (acceptors) that lead to increase of an electronic polarizability of such molecules. Thus a distribution of electronic density in the molecules is non-uniform. Presence of the electro-conductive oligomers leads to increasing of polarization ability of the disclosed electro-polarizable compound because of electronic super conductivity of the electro-conductive oligomers. Ionic groups increase an ionic component of polarization of the disclosed electro-polarizable compound. The nonlinearly polarizable fragments comprising an aromatic polycyclic conjugated molecule with at least one dopant group, the electro-conductive oligomers and the ionic groups are placed into the resistive dielectric envelope formed by resistive substituents providing solubility of the organic compound in a solvent and electrically insulating the column-like supramolecules from each other. A non-centrosymmetric arrangement of the dopant group(s) can lead to a strong nonlinear response of the compound's electronic polarization in the presence of an electric field. The resistive substituents increase the electric strength of these electro-polarizable compounds and breakdown voltage of the dielectric layers made on their basis.

[0031] In one embodiment of the present disclosure, the aromatic polycyclic conjugated molecule (Core1) comprises rylene fragments. In another embodiment of the disclosed electro-polarizable compound, the rylene fragments are selected from structures from 1 to 12 as given in Table 1.

TABLE-US-00001 TABLE 1 Examples of the aromatic polycyclic conjugated molecule comprising rylene fragments [00004] 1 [00005] 2 [00006] 3 [00007] 4 [00008] 5 [00009] 6 [00010] 7 [00011] 8 [00012] 9 [00013] 10 [00014] 11 [00015] 12

[0032] In yet another embodiment of the electro-polarizable compound, the aromatic polycyclic conjugated molecule (Core1) is tetrapirolic macro-cyclic fragment. In still another embodiment of the electro-polarizable compound, the tetrapirolic macro-cyclic fragments have a general structural formula from the group comprising structures 13-19 as given in Table 2, where M denotes an atom of metal or two protons (2H).

TABLE-US-00002 TABLE 2 Examples of the aromatic polycyclic conjugated molecule comprising tetrapirolic macro-cyclic fragment [00016] 13 [00017] 14 [00018] 15 [00019] 16 [00020] 17 [00021] 18 [00022] 19

[0033] In one embodiment of the present disclosure, the dopant group (R1) is selected from nucleophilic groups (donors) and electrophilic groups (acceptors). The electrophilic groups (acceptors) are selected from NO.sub.2, NH.sub.3.sup.+ and NR.sub.3.sup.+ (quaternary nitrogen salts), counterion Cl.sup. or Br.sup., CHO (aldehyde), CRO (keto group), SO.sub.3H (sulfonic acids), SO.sub.3R (sulfonates), SO.sub.2NH.sub.2 (sulfonamides), COOH (carboxylic acid), COOR (esters, from carboxylic acid side), COCl (carboxylic acid chlorides), CONH.sub.2 (amides, from carboxylic acid side), CF.sub.3, CCl.sub.3, CN, wherein R is radical selected from the list comprising alkyl (methyl, ethyl, isopropyl, tert-butyl, neopentyl, cyclohexyl etc.), allyl (CH.sub.2CHCH.sub.2), benzyl (CH.sub.2C.sub.6H.sub.5) groups, phenyl (+substituted phenyl) and other aryl (aromatic) groups. The nucleophilic groups (donors) are selected from O.sup. (phenoxides, like ONa or OK), NH.sub.2, NHR, NR.sub.2, OH, OR (ethers), NHCOR (amides, from amine side), OCOR (esters, from alcohol side), alkyls, C.sub.6H.sub.5, vinyls, wherein R is radical selected from the list comprising alkyl (methyl, ethyl, isopropyl, tert-butyl, neopentyl, cyclohexyl etc.), allyl (CH2-CHCH2), benzyl (CH2C6H5) groups, phenyl (+substituted phenyl) and other aryl (aromatic) groups.

[0034] In another embodiment of the present disclosure, the electro-conductive oligomer (Core2) is selected from the structures 20 to 28 as given in Table 3, wherein I=2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, Z is O, S or NR5, and R5 is selected from the group consisting of unsubstituted or substituted C.sub.1-C.sub.18alkyl, unsubstituted or substituted C.sub.2-C.sub.18alkenyl, unsubstituted or substituted C.sub.2-C.sub.18alkynyl, and unsubstituted or substituted C.sub.4-C.sub.18aryl.

TABLE-US-00003 TABLE 3 Examples of the polycyclic organic compound comprising electro-conductive oligomer [00023] 20 [00024] 21 [00025] 22 [00026] 23 [00027] 24 [00028] 25 [00029] 26 [00030] 27 [00031] 28

[0035] In yet another embodiment of the disclosed electro-polarizable compound, at least one ionic group R2 or R3 is independently 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 list comprising H, alkyl, and fluorine. In still another embodiment of the disclosed electro-polarizable compound, at least one connecting group is selected from the list comprising the following structures: 29-39 given in Table 4, where W is hydrogen (H) or an alkyl group.

TABLE-US-00004 TABLE 4 Examples of the connecting group O 29 [00032] 30 [00033] 31 [00034] 32 [00035] 33 [00036] 34 [00037] 35 [00038] 36 [00039] 37 [00040] 38 [00041] 39

[0036] In one embodiment of the present disclosure, the at least one connecting group is selected from the group of CH.sub.2, CF.sub.2, SiR.sub.2O, CH.sub.2CH.sub.2O, wherein R is selected from the list comprising H, alkyl, and fluorine. In another embodiment of the present disclosure, the at least one connecting group is selected from structures 40 to 45 as given in table 5.

TABLE-US-00005 TABLE 5 Examples of the connecting group [00042] 40 [00043] 41 [00044] 42 [00045] 43 [00046] 44 [00047] 45

[0037] In yet another embodiment of the present disclosure, the resistive substituent R4 is selected from the group of alkyl, aryl, substituted alkyl, substituted aryl, fluorinated alkyl, chlorinated alkyl, branched and complex alkyl, branched and complex fluorinated alkyl, branched and complex chlorinated alkyl groups, and any combination thereof, and wherein the alkyl group is selected from methyl, ethyl, propyl, n-butyl, iso-butyl and tert-butyl groups, and the aryl group is selected from phenyl, benzyl and naphthyl groups or siloxane, and/or polyethyleneglycol as linear or branched chains. In still another embodiment of the present disclosure, the resistive substituent R4 is C.sub.XQ.sub.2X+1, where X1 and Q is hydrogen (H), fluorine (F), or chlorine (Cl).

[0038] In one embodiment of the electro-polarizable compound, the aromatic polycyclic conjugated molecule (Core1) and the dopant groups (R1) form a non-centrosymmetric molecular structure. In another embodiment of the electro-polarizable compound, the aromatic polycyclic conjugated molecule (Core1), the dopant groups (R1) and the resistive substituents (R4) form a non-centrosymmetric molecular structure.

[0039] In one embodiment of the present disclosure, the electro-polarizable compound has the following general formula (II):

##STR00048##

[0040] The aromatic polycyclic conjugated molecule (Core1) is rylene fragment having following structural formula:

##STR00049##

[0041] Two (m is equal to 2) dopant groups NH.sub.2 and NO.sub.2 are located on rylene phenyl rings and/or apex phenyl ring of Core1. The electro-conductive oligomer (Core2) has following structural formula wherein I=2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12:

##STR00050##

[0042] The number n of the electro-conductive oligomers is equal to 2 and the two Core2 are located in apex positions of the Core1, R3 is the ionic group [SO.sub.3].sup., the number s of the ionic groups R3 is equal to 2, the ionic groups are connected to the electro-conductive oligomer (Core2) via a connecting group having following structural formula:

##STR00051##

The group R4 is C.sub.18H.sub.37-resistive substituent located in side (lateral) position of the Core2.

[0043] In another embodiment of the present disclosure, the electro-polarizable compound has the following general formula (III):

##STR00052##

[0044] The aromatic polycyclic conjugated molecule (Core1) is a tetrapirolic macro-cyclic fragment having the following structural formula:

##STR00053##

In this example, there are two dopant groups so m is equal to 2. The two dopant groups NH.sub.2 and NO.sub.2 are located on opposite apex positions of the Core1, the electro-conductive oligomer (Core2) has following structural formula, wherein I=2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12:

##STR00054##

The number n of the electro-conductive oligomers is equal to 2 and the two Core2 are located in apex positions of the Core1, R3 is the ionic group COO.sup., number s of the ionic groups R3 is equal to 2, the ionic groups are connected to the electro-conductive oligomer (Core2) via a connecting group having following structural formula:

##STR00055##

The group R4 is (C.sub.1-C.sub.20)alkyl-resistive substituent located in side (lateral) position of the Core2.

[0045] In another embodiment of the electro-polarizable compound, a fragment comprising the aromatic polycyclic conjugated molecule (Core1), dopant groups (R1) and/or resistive substituents providing solubility of the organic compound in a solvent and electrically insulating the column-like supramolecules from each other (R4) is selected from structures 46 to 97 as given in Table 6.

TABLE-US-00006 TABLE 6 Examples of the fragment comprising the aromatic polycyclic conjugated molecule (Core1) [00056] 46 [00057] 47 [00058] 48 [00059] 49 [00060] 50 [00061] 51 [00062] 52 [00063] 53 [00064] 54 [00065] 55 [00066] 56 [00067] 57 [00068] 58 [00069] 59 [00070] 60 [00071] 61 [00072] 62 [00073] 63 [00074] 64 [00075] 65 [00076] 66 [00077] 67 [00078] 68 [00079] 69 [00080] 70 [00081] 71 [00082] 72 [00083] 73 [00084] 74 [00085] 75 [00086] 76 [00087] 77 [00088] 78 [00089] 79 [00090] 80 [00091] 81 [00092] 82 [00093] 83 [00094] 84 [00095] 85 [00096] 86 [00097] 87 [00098] 88 [00099] 89 [00100] 90 [00101] 91 [00102] 92 [00103] 93 [00104] 94 [00105] 95 [00106] 96 [00107] 97 [00108]

[0046] In yet another embodiment of the electro-polarizable compound, a fragment comprising the electro-conductive oligomer (Core2), resistive substituents providing solubility of the organic compound in a solvent and electrically insulating the column-like supramolecules from each other (R4) and/or the ionic groups R3 is selected from structures 98 to 107 as given in Table 7:

TABLE-US-00007 TABLE 7 Examples of the fragment comprising the electro-conductive oligomer (Core2) [00109] 98 [00110] 99 [00111] 100 [00112] 101 [00113] 102 [00114] 103 [00115] 104 [00116] 105 [00117] 106 [00118] 107

[0047] In one embodiment of the present disclosure, a polarization () of the electro-polarizable compound comprises first-order (.sup.(1)) and second-order (.sup.(2)) polarization according to follow formula: =.sup.(1)+.sup.(2).Math.E, where E is an intensity of external electric field.

[0048] In one aspect, the present disclosure provides the organic solvent comprising the disclosed electro-polarizable compound. In one embodiment of the present disclose, the solution comprises a mixture of different electro-polarizable compounds. In another embodiment of the disclosed organic solvent, the mixture of the electro-polarizable compounds comprises the rylene fragments of different length. In one embodiment of disclosed organic solvent, the organic solvent is selected from the list comprising ketones, carboxylic acids, hydrocarbons, cyclic hydrocarbons, chlorohydrocarbons, alcohols, ethers, esters, and any combination thereof. In another embodiment of disclosed organic solvent, 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 disclose, the solution is a lyotropic liquid crystal solution.

[0049] In another aspect, the present disclosure provides a crystal metadielectric layer comprising at least one type of the disclosed electro-polarizable compounds. The crystal metadielectric layers are produced from the disclosed organic compound by the Cascade Crystallization.

[0050] Cascade Crystallization process involves a chemical modification step and four steps of ordering during the crystal metadielectric layer formation. The chemical modification step introduces hydrophilic groups on the periphery of the molecule of the disclosed organic compound in order to impart amphiphilic properties to the molecule. Amphiphilic molecules stack together into supramolecules, which is the first step of ordering. At certain concentration, supramolecules are converted into a liquid-crystalline state to form a lyotropic liquid crystal, which is the second step of ordering. The lyotropic liquid crystal is deposited under the action of a shear force (or meniscus force) onto a substrate based on a Mayer Rod shearing technique, so that shear force (or the meniscus) direction determines the crystal axis direction in the resulting solid crystal layer. The external alignment upon the lyotropic liquid crystal can be produced using any other means, for example by applying an external electric field at normal or elevated temperature, with or without additional illumination, magnetic field, or optical field (e.g., coherent photovoltaic effect); the degree of the external alignment should be sufficient to impart necessary orientation to the supramolecules of the lyotropic liquid crystal and form a structure, which serves as a base of the crystal lattice of the crystal dielectric layer. This directional deposition is third step of ordering, representing the global ordering of the crystalline or polycrystalline structure on the substrate surface. The last fourth step of the Cascade Crystallization process is drying/crystallization, which converts the lyotropic liquid crystal into a solid crystal dielectric layer. The term Cascade Crystallization process is used to refer to the chemical modification and four ordering steps as a combination process.

[0051] The Cascade Crystallization process is used for production of thin crystalline metadielectric layers. The dielectric layer produced by the Cascade Crystallization process has a global order which means that a direction of the crystallographic axis of the layer over the entire substrate surface is controlled by the deposition process. Molecules of the deposited material are packed into supramolecules with a limited freedom of diffusion or motion. The thin crystalline dielectric layer is characterized by an interplanar spacing of 3.40.3 ngstrms () in the direction of one of the optical axes.

[0052] In one embodiment of the present disclosure, the crystal metadielectric layer comprises the column-like supramolecules formed by the electro-polarizable compounds comprising the rylene fragments of different length. The variety of the rylene fragment lengths increases the randomness of the stack. In one embodiment of the present disclosure, the layer's relative permittivity is greater than or equal to 1000. In another embodiment of the present disclosure, the polarization (P) of the crystal metadielectric layer comprises first-order (.sub.(1)) and second-order (.sub.(2)) and third order (.sub.(3)) permittivities according to the following formula:

P=.sub.0(.sub.11)E+.sub.0.sub.2E.sup.2+.sub.0.sub.3E.sup.3+ . . .

[0053] where P is the polarization of the material, which also can be represented by the following formula:

P=NP.sub.induced

[0054] where P.sub.induced is the induced polarization which can be expressed by the formula:

P.sub.induced=E.sub.loc+E.sub.loc.sup.2+E.sub.loc.sup.3+ . . .

[0055] where E.sub.loc is the localized field and is expressed by the formula:

E.sub.loc=E+P/(3.sub.0)

[0056] The real part of the relative permittivity () as can be seen from the above equations, also comprises first, second, and third order permittivities. Further, permittivity of a capacitor is a function of applied voltage and thickness of the capacitor's dielectric (d). Where voltage is the DC-voltage which is applied to the crystal metadielectric layer, and d is the layer thickness. In another embodiment of the present invention, the layer's resistivity is greater than or equal to 10.sup.13 ohm/cm.

[0057] 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 metadielectric layer between said electrodes. The layer comprises the electro-polarizable compounds as disclosed above.

[0058] The meta-capacitor comprises a first electrode 1, a second electrode 2, and a metadielectric layer 3 disposed between said first and second electrodes as shown in FIG. 1A. The electrodes 1 and 2 may be made of a metal, such as copper, zinc, or aluminum or other conductive material such as graphite or carbon nanomaterials and are generally planar in shape.

[0059] The electrodes 1, 2 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 1 and 2 may range from about 100 nm to about 10 000 m. The maximum voltage V.sub.bd between the electrodes 1 and 2 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 1 and 2 is 10,000 microns (100,000 nm), the maximum voltage V.sub.bd would be 100,000 volts.

[0060] The electrodes 1 and 2 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 1 and 2 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.

[0061] 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.

[0062] 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(V)

where .sub.0 is the permittivity of free space (8.8510.sup.12 Coulombs.sup.2/(Newton.Math.meter.sup.2)) and is the dielectric constant of the dielectric layer. The energy storage capacity U of the capacitor may be approximated as:

U=1/2 .sub.0AE.sub.bd.sup.2(VI)

[0063] The energy storage capacity U is determined by the dielectric constant E, 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.

[0064] 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.

[0065] The present disclosure includes meta-capacitors that are coiled, e.g., as depicted in FIG. 1B. In this example, a meta-capacitor 20 comprises a first electrode 21, a second electrode 22, and a metadielectric material layer 23 of the type described hereinabove disposed between said first and second electrodes. The electrodes 21 and 22 may be made of a metal, such as copper, zinc, or aluminum or other conductive material such as graphite or carbon nanomaterials and are generally planar in shape. In one implementation, the electrodes and metadielectric material layer 23 are in the form of long strips of material that are sandwiched together and wound into a coil along with an insulating material, e.g., a plastic film such as polypropylene or polyester to prevent electrical shorting between the electrodes 21 and 22.

[0066] In order that the invention may be more readily understood, reference is made to the following examples, which are intended to be illustrative of the invention, but are not intended to limit the scope.

Example 1

[0067] ##STR00119##

Procedure:

[0068] ##STR00120##

[0069] To H.sub.2O (10.0 mL) was added NaHCO.sub.3 (1.7 g, 20.2 mmol, 30 g/mol equiv.) and NaBr (280.0 mg, 2.7 mmol, 5 g/mol equiv.). The mixture was stirred to form a clear solution. Compound 1 (20 g, 56.4 mmol, 1 equiv.) in Dichloromethane (DCM) (70 mL) and tempo (340.0 mg, 0.6 g/mol) were added to the clear solution. The two-phase mixture was cooled down to 10 C. using an ice bath. The NaClO solution (70.5 mL, 0.8 N, 1 equiv.) was added dropwise with vigorous stirring. After the NaClO solution was added, the mixture was removed from the ice bath and stirred at room temperature for 30 min. The DCM phase was collected, extracted with DCM (25 mL2), combined with organic phase, washed with water and brine, dried over MgSO.sub.4, and was concentrated to give compound 2 18 g (90%) as a colorless oil. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.

##STR00121##

[0070] To DCM (500 mL) was added PPh.sub.3 (154.0 g, 587 mmol, 4 equiv.) under N.sub.2 atmosphere. To the suspension was added CBr.sub.4 (97.3 g, 294 mmol, 2 equiv.) at 0 C. The mixture was stirred for 15 min at 0 C. and 20 min at room temperature. Freshly made compound 2 (51.4 g, 146 mmol, 1.0 equiv.) in DCM (150 mL) was added dropwise to the mixture. The mixture was stirred at room temperature for 6 hrs. Hexanes (1 L) was added. The solid was filtered off. The filtrate was concentrated. The residue was separated through a column to afford compound 3 57.0 g (79% in 2 steps) as colorless oil. .sup.1H NMR (300 MHz, CDCl.sub.3) 0.88 (t, 6H), 1.26 (m, 28H), 2.35 (m, 1H), 6.10 (d, 1H).

##STR00122##

[0071] To anhydrous Tetrahydrofuran (THF) (250 mL) was added compound 3 (57.0 g, 115 mmol, 1 equiv.). The mixture was cooled down to 78 C. under N.sub.2-atmosphere. n-BuLi (138 mL, 2.5 M, 3 equiv.) was added dropwise to the mixture. The mixture was stirred for 2 hours, then was quenched with water (200 mL). The organic phase was collected. The water phase was extracted with EA (50 mL2). The organic phases were combined, washed with water and brine, dried over MgSO.sub.4 and concentrated to afford crude compound 4 37.1 g (100%) as colorless oil. .sup.1H NMR (300 MHz, CDCl.sub.3) 0.88 (t, 6H), 1.26 (m, 28H), 2.30 (m, 1H), 2.03 (s, 1H).

##STR00123##

[0072] To EtOH (40.0 mL) was added compound 6 (4.2 g, 23.0 mmol, 1.0 equiv.), AgSO.sub.4 (10.0 g, 32.1 mmol, 1.4 equiv.) and I.sub.2 (8.2 g, 32.1 mmol, 1.4 equiv.). The mixture was stirred at room temperature for 18 hrs. Solid material was filtered off and washed with ethyl acetate (EA), and the filtrate was concentrated. The residue was separated through a column to afford compound 7 5.4 g (77%) as a dark yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.

[0073] Scale up: To Ethanol (EtOH) (1000.0 mL) was added compound 6 (100.0 g, 547.6 mmol, 1.0 equiv.), AgSO.sub.4 (238.0 g, 764.3 mmol, 1.4 equiv.) and I.sub.2 (195.2 g, 764.3 mmol, 1.4 equiv.). The mixture was stirred at room temperature for 18 hrs. Solid material was filtered off and washed with EA (200 mL2). The filtrate was concentrated until of the filtrate volume remained. The solid was filtered and washed by cold EtOH (100 mL2) to provide compound 7 43 g as dark yellow solid with less than 5% starting material 6 inside. The filtrate was concentrated and the above described procedure was repeated with 0.7 equiv. of AgSO.sub.4 and I.sub.2. The same working up process was applied to resulting second batch of compound 7 30 g as dark yellow solid with less than 5% starting material 6 inside. The solids were combined to afford compound 7 73 g (43.4%). .sup.1H NMR (300 MHz, CDCl.sub.3) not available. Reaction was tracked by TLC.

##STR00124##

[0074] To anhydrous THF (10.0 mL) and tri-ethyl amine (10.0 mL) was added compound 4 (7.4 g, 21.2 mmol, 1.2 equiv.), compound 7 (5.2 g, 16.7 mmol, 1.0 equiv.), Pd(dppf)Cl.sub.2 (0.05 g, 0.08 mmol, 0.02 equiv.), CuI (0.02 g, 0.1 mmol, 0.04 equiv.). The mixture was degassed under vacuum and purged with N.sub.2 three times. The reaction was stirred at 70 C. for 8.0 hours. The mixture was cooled down to room temperature and EA (10 mL) was added to dilute. The solid was filtered off and the filtrate was concentrated, then separated with a column to afford compound 5 7.5 g (84%) as a yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3)) 7.99 (s, 2H), 2.45 (m, 1H), 1.26-1.55 (m, 40H), 0.87 (t, 6H).

##STR00125##

[0075] To EtOH (20.0 mL) was added compound 5 (7.5 g, 14.1 mmol, 1.0 equiv.) and ammonium sulfide (8.6 g 20% water solution, 28.2 mmol, 2.0 equiv.). The mixture was stirred at 80 C. for 1 hour. 2.0 equivalents of ammonium sulfide were added again. The mixture was stirred at 80 C. for an additional 1 hour. The mixture was concentrated, diluted with EA, and washed with water and brine. The organic phase was collected, concentrated and separated through a column to give product 8 6.1 g (87%) as a dark red solid. .sup.1H NMR (300 MHz, CDCl.sub.3) 7.81 (s, 1H), 6.94 (s, 1H), 2.45 (m, 1H), 1.26-1.46 (m, 40H), 0.87 (t, 6H).

##STR00126##

[0076] To a 25 mL flask was added compound 8 (1 equiv.), 4-bromo-1,8-naphthalic anhydride (1 equiv.) and imidazole (70 equiv.). The mixture was degassed under vacuum and purged with N.sub.2 three times. The reaction was stirred at 130 C. for 3 hours and 180 C. for 12 more hours. The dark purple mixture was cooled down. The solid was washed with water (360 mL) and EtOH (360 mL), and vacuum dried to give 9.

##STR00127##

[0077] To EtOH (20.0 mL) was added compound 9 (1.0 equiv.) and ammonium sulfide (2.0 equiv.). The mixture was stirred at 80 C. for 1 hour. 2.0 equivalents of ammonium sulfide were added again. The mixture was stirred at 80 C. for an additional 1 hour. The mixture was concentrated, diluted with EA, washed with water and brine, and dried to give 10.

##STR00128##

[0078] A deaerated mixture of 9 (2.0 mmol), boronic acid dimer (2.0 mmol), and Pd(Ph).sub.4 (4.Math.10-2 mmol) in aq. Na2CO3 (1.4 M, 15 ml) was held at 65 C. for 9 hours. Thereafter, the reaction mixture was cooled and extracted with chloroform (315 ml). The organic phase was dried over anhydrous MgSO4 and concentrated in vacuo to give 11.

##STR00129##

[0079] A deaerated mixture of 10 (2.0 mmol), 11 (2.0 mmol), and Pd(Ph).sub.4 (4.Math.10-2 mmol) in aq. Na2CO3 (1.4 M, 15 ml) was held at 65 C. for 9 hours. Thereafter, the reaction mixture was cooled and extracted with chloroform (315 ml). The organic phase was dried over anhydrous MgSO4 and concentrated in vacuo to give 12.

##STR00130##

[0080] A mixture of 1.48 g (13 mmol) potassium tert-butoxide 2.30 g (15.1 mmol) of diazabicyclo[5.4.0]undec-7-ene (DBU), 2.2 g 36.3 mmol) ethanolamine and 1.0 g of 12 was heated to 140 C. for 11 hours. Afterwards, the same amount of potassium tert-butylat, DBU and ethanolamine were added and the mixture was kept at 140 C. for 18 hours. The reaction mixture was cooled to room temperature, poured into 250 ml of 1M HCl filtered, washed until neutral pH and then dried to give the final product.

Example 2

[0081] ##STR00131##

Procedure:

[0082] ##STR00132##

[0083] To EtOH (40.0 mL) was added compound 6 (4.2 g, 23.0 mmol, 1.0 equiv.), AgSO.sub.4 (10.0 g, 32.1 mmol, 1.4 equiv.) and I.sub.2 (8.2 g, 32.1 mmol, 1.4 equiv.). The mixture was stirred at room temperature for 18 hrs. The solid was filtered off and washed with EA. The filtrate was concentrated. The residue was separated through a column to afford compound 7 5.4 g (77%) as a dark yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.

[0084] Scale up: To EtOH (1000.0 mL) was added compound 6 (100.0 g, 547.6 mmol, 1.0 equiv.), AgSO.sub.4 (238.0 g, 764.3 mmol, 1.4 equiv.) and I.sub.2 (195.2 g, 764.3 mmol, 1.4 equiv.). The mixture was stirred at room temperature for 18 hours. The solid was filtered off and washed with EA (200 mL2). The filtrate was concentrated until of the filtrate volume remained. The solid was filtered and washed by cold EtOH (100 mL2) to provide compound 7 43 g as dark yellow solid with less than 5% starting material 6 inside. The filtrate was concentrated and the above-described procedure was repeated with 0.7 equiv. of AgSO.sub.4 and I.sub.2. The same working up process was applied to provided second batch of compound 7 30 g as dark yellow solid with less than 5% starting material 6 inside. The solids were combined to afford compound 7 73 g (43.4%). .sup.1H NMR (300 MHz, CDCl.sub.3) not available. Reaction was tracked by TLC.

##STR00133##

[0085] To anhydrous THF (10.0 mL) and TEA (10.0 mL) was added compound didodecylamine (1.2 equiv.), compound 7 (1.0 equiv.), Pd(dppf)Cl.sub.2 (0.02 equiv.), CuI (0.04 equiv.). The mixture was degassed under vacuum and purged with N.sub.2 three times. The reaction was stirred at 70 C. for 8.0 hrs. The mixture was cooled down and EA (10 mL) was added to dilute. The solid was filtered off and the filtrate was concentrated, then separated with a column to afford compound 15.

##STR00134##

[0086] To EtOH (20.0 mL) was added compound 15 (7.5 g, 14.1 mmol, 1.0 equiv.) and ammonium sulfide (8.6 g 20% water solution, 28.2 mmol, 2.0 equiv.). The mixture was stirred at 80 C. for 1 hour. 2.0 equivalents of ammonium sulfide were added again. The mixture was stirred 80 C. for an additional 1 hour. The mixture was concentrated, diluted with EA, washed with water and brine. The organic phase was collected, concentrated and separated through a column to give product 16.

##STR00135##

[0087] To a 25 mL flask was added compound 16 (1 equiv.), 4-bromo-1,8-naphthalic anhydride (1 equiv.) and imidazole (70 equiv.). The mixture was degassed under vacuum and purged with N.sub.2 three times. The reaction was stirred at 130 C. for 3 hours and 180 C. for 12 more hours. The dark purple mixture was cooled down. The solid was washed with water (360 mL) and EtOH (360 mL), and vacuum dried to give 17.

##STR00136##

[0088] To EtOH (20.0 mL) was added compound 17 (1.0 equiv.) and ammonium sulfide (2.0 equiv.). The mixture was stirred at 80 C. for 1 hour. Refilled 2.0 equiv. ammonium sulfide. The mixture was stirred at 80 C. for an additional 1 hour. The mixture was concentrated, diluted with EA, washed with water and brine, and dried to give 18a.

##STR00137##

[0089] A deaerated mixture of 17 (2.0 mmol), boronic acid dimer (2.0 mmol), and Pd(Ph).sub.4 (4.Math.10-2 mmol) in aq. Na2CO3 (1.4 M, 15 ml) was held at 65 C. for 9 hours. Thereafter, the reaction mixture was cooled and extracted with chloroform (315 ml). The organic phase was dried over anhydrous MgSO4 and concentrated in vacuo to give 18b.

##STR00138##

[0090] A deaerated mixture of 18a (2.0 mmol), 18b (2.0 mmol), and Pd(Ph).sub.4 (4.Math.10-2 mmol) in aq. Na2CO3 (1.4 M, 15 ml) was held at 65 C. for 9 hours. Thereafter, the reaction mixture was cooled and extracted with chloroform (315 ml). The organic phase was dried over anhydrous MgSO4 and concentrated in vacuo to give 19.

##STR00139##

[0091] A mixture of 1.48 g (13 mmol) potassium tert-butoxide 2.30 g (15.1 mmol) of diazabicyclo[5.4.0]undec-7-ene (DBU), 2.2 g 36.3 mmol) ethanolamine and 1.0 g of 19 was heated to 140 C. for 11 hours. Afterwards, the same amount of potassium tert-butylat, DBU and ethanolamine were added and the mixture was kept at 140 C. for 18 hours. The reaction mixture was cooled to room temperature, poured into 250 ml of 1M HCl, filtered, washed until neutral pH and then dried to give the final product.

Example 3

[0092] ##STR00140##

Procedure:

[0093] ##STR00141##

[0094] To H.sub.2O (10.0 mL) was added NaHCO.sub.3 (1.7 g, 20.2 mmol, 30 g/mol equiv.) and NaBr (280.0 mg, 2.7 mmol, 5 g/mol equiv.). The mixture was stirred to form a clear solution. Compound 1 (20 g, 56.4 mmol, 1 equiv.) in DCM (70 mL) and tempo (340.0 mg, 0.6 g/mol) were added to the clear solution. The two-phase mixture was cooled down to 10 C. using an ice bath. The NaClO solution (70.5 mL, 0.8 N, 1 equiv.) was added drop-wise with vigorous stirring. After addition, the NcClO mixture was removed from the ice bath and kept stirred at room temperature for 30 min. The DCM phase was collected, extracted with DCM (25 mL2), combined with organic phase, washed with water and brine, dried over MgSO.sub.4, and was concentrated to give compound 2 18 g (90%) as a colorless oil. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.

##STR00142##

[0095] To DCM (500 mL) was added PPh.sub.3 (154.0 g, 587 mmol, 4 equiv.) under N.sub.2-atmosphere. To the suspension was added CBr.sub.4 (97.3 g, 294 mmol, 2 equiv.) at 0 C. The mixture was stirred for 15 min at 0 C. and 20 min at rt. Freshly made compound 2 (51.4 g, 146 mmol, 1.0 equiv.) in DCM (150 mL) was added dropwise. The mixture was stirred at room temperature for 6 hrs. Hexanes (1 L) was added. The solid was filtered off. The filtrate was concentrated. The residue was separated through a column to afford compound 3 57.0 g (79% in 2 steps) as colorless oil. .sup.1H NMR (300 MHz, CDCl.sub.3) 0.88 (t, 6H), 1.26 (m, 28H), 2.35 (m, 1H), 6.10 (d, 1H).

##STR00143##

[0096] To anhydrous THF (250 mL) was added compound 3 (57.0 g, 115 mmol, 1 equiv.). The mixture was cooled down to 78 C. under N.sub.2-atmosphere. n-BuLi (138 mL, 2.5 M, 3 equiv.) was added dropwise. The mixture was stirred for 2 hours, then was quenched with water (200 mL). The organic phase was collected. The water phase was extracted with EA (50 mL2). The organic phases were combined, washed with water and brine, dried over MgSO.sub.4 and concentrated to afford crude compound 4 37.1 g (100%) as colorless oil. .sup.1H NMR (300 MHz, CDCl.sub.3) 0.88 (t, 6H), 1.26 (m, 28H), 2.30 (m, 1H), 2.03 (s, 1H).

##STR00144##

[0097] To EtOH (40.0 mL) was added compound 6 (4.2 g, 23.0 mmol, 1.0 equiv.), AgSO.sub.4 (10.0 g, 32.1 mmol, 1.4 equiv.) and I.sub.2 (8.2 g, 32.1 mmol, 1.4 equiv.). The mixture was stirred at room temperature for 18 hrs. Solid material was filtered and washed with EA. The filtrate was concentrated. The residue was separated through a column to afford compound 7 5.4 g (77%) as a dark yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.

[0098] Scale up: To EtOH (1000.0 mL) was added compound 6 (100.0 g, 547.6 mmol, 1.0 equiv.), AgSO.sub.4 (238.0 g, 764.3 mmol, 1.4 equiv.) and I.sub.2 (195.2 g, 764.3 mmol, 1.4 equiv.). The mixture was stirred at room temperature for 18 hrs. The solid material was filtered, washed with EA (200 mL2). The filtrate was concentrated till volume. The solid was filtered and washed by cold EtOH (100 mL2) to provide compound 7 43 g as dark yellow solid with less than 5% starting material 6 inside. The filtrate was concentrated and the above-described procedure was repeated with 0.7 equivalent of AgSO.sub.4 and I.sub.2. The same working up process was applied to provide second batch of compound 7 30 g as dark yellow solid with less than 5% starting material 6 inside. The solids were combined to afford compound 7 73 g (43.4%). .sup.1H NMR (300 MHz, CDCl.sub.3) not available. Reaction was tracked by TLC.

##STR00145##

[0099] To anhydrous THF (10.0 mL) and TEA (10.0 mL) was added compound 4 (7.4 g, 21.2 mmol, 1.2 equiv.), compound 7 (5.2 g, 16.7 mmol, 1.0 equiv.), Pd(dppf)Cl.sub.2 (0.05 g, 0.08 mmol, 0.02 equiv.), CuI (0.02 g, 0.1 mmol, 0.04 equiv.). The mixture was degassed under vacuum and purged with N.sub.2 three times. The reaction was stirred at 70 C. for 8.0 hours. The mixture was cooled down and EA (10 mL) was added to dilute. The solid was filtered off and the filtrate was concentrated, then separated with a column to afford compound 5 7.5 g (84%) as a yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3) 7.99 (s, 2H), 2.45 (m, 1H), 1.26-1.55 (m, 40H), 0.87 (t, 6H).

##STR00146##

[0100] To EtOH (20.0 mL) was added compound 5 (7.5 g, 14.1 mmol, 1.0 equiv.) and ammonium sulfide (8.6 g 20% water solution, 28.2 mmol, 2.0 equiv.). The mixture was stirred at 80 C. for 1 hour. 2.0 equivalents of ammonium sulfide were added again. The mixture was stirred at 80 C. for an additional 1 hour. The mixture was concentrated, diluted with EA, washed with water and brine. The organic phase was collected, concentrated and separated through a column to give product 8 6.1 g (87%) as a dark red solid. .sup.1H NMR (300 MHz, CDCl.sub.3) 7.81 (s, 1H), 6.94 (s, 1H), 2.45 (m, 1H), 1.26-1.46 (m, 40H), 0.87 (t, 6H).

##STR00147##

[0101] To a 25 mL flask was added compound 8 (5.1 g, 10.2 mmol, 2.2 equiv.), 3,4-perylene anhydride (4.6 mmol, 1 equiv.) and imidazole (21 g, 324.5 mmol, 70 equiv.). The mixture was degassed under vacuum and purged with N.sub.2 three times. The reaction was stirred at 130 C. for 3 hours and 180 C. for 12 more hours. The dark purple mixture was cooled down. The solid was washed with water (360 mL) and EtOH (360 mL), and vacuum dried to give 13.

##STR00148##

[0102] To EtOH (20.0 mL) was added compound 13 (14.1 mmol, 1.0 equiv.) and ammonium sulfide (28.2 mmol, 2.0 equiv.). The mixture was stirred at 80 C. for 1 hr. Refilled 2.0 equiv. ammonium sulfide. Stirring continued at 80 C. for 1 hr. The mixture was concentrated, diluted with EA, washed with water and brine, and dried to give 14.

##STR00149##

[0103] A mixture of 1.48 g (13 mmol) potassium tert-butoxide, 2.30 g (15.1 mmol) of diazabicyclo[5.4.0]undec-7-ene (DBU) 36.3 mmol) ethanolamine and 1.0 equiv. uiv. of 13 and 1.0 equiv. uiv. of 14 was heated to 140 C. for 11 h. Afterwards, the same amount of potassium tert-butylate, DBU and ethanolamine were added and the mixture was kept at 140 C. for 18 hours. The reaction mixture was cooled to room temperature, poured into 250 ml of 1M HCl filtered, washed until neutral pH and then dried to give the final product as a mixture of isomers.

Example 4

[0104] ##STR00150##

Procedure:

[0105] ##STR00151##

[0106] To H.sub.2O (10.0 mL) was added NaHCO.sub.3 (1.7 g, 20.2 mmol, 30 g/mol eq) and NaBr (280.0 mg, 2.7 mmol, 5 g/mol eq). The mixture was stirred to form a clear solution. Compound 1 (20 g, 56.4 mmol, 1 eq) in DCM (70 mL) and tempo (340.0 mg, 0.6 g/mol) were added to the clear solution. The two-phase mixture was cooled down to 10 C. The NaClO solution (70.5 mL, 0.8 N, 1 eq) was added dropwise with vigorously stirring. After addition, removed ice bath and kept stirring at room temperature for 30 min. The DCM phase was collected, extracted with DCM (25 mL2), combined with organic phase, washed with water and brine, dried over MgSO.sub.4, and was concentrated to give compound 2 18 g (90%) as a colorless oil. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.

##STR00152##

[0107] To DCM (500 mL) was added PPh.sub.3 (154.0 g, 587 mmol, 4 eq) under N.sub.2-atmosphere. To the suspension was added CBr.sub.4 (97.3 g, 294 mmol, 2 eq) at 0 C. The mixture was stirred for 15 min at 0 C. and 20 min at room temperature. Freshly made compound 2 (51.4 g, 146 mmol, 1.0 eq) in DCM (150 mL) was added dropwise. The mixture was stirred at room temperature for 6 hours. Hexanes (1 L) was added. The solid was filtered off. The filtrate was concentrated. The residue was separated through a column to afford compound 3 57.0 g (79% in 2 steps) as colorless oil. .sup.1H NMR (300 MHz, CDCl.sub.3) 0.88 (t, 6H), 1.26 (m, 28H), 2.35 (m, 1H), 6.10 (d, 1H).

##STR00153##

[0108] To anhydrous THF (250 mL) was added compound 3 (57.0 g, 115 mmol, 1 eq). The mixture was cooled down to 78 C. under N.sub.2-atmosphere. n-BuLi (138 mL, 2.5 M, 3 eq) was added dropwise. The mixture was stirred for 2 hours, then was quenched with water (200 mL). The organic phase was collected. The water phase was extracted with EA (50 mL2). The organic phases were combined, washed with water and brine, dried over MgSO.sub.4 and concentrated to afford crude compound 4 37.1 g (100%) as colorless oil. .sup.1H NMR (300 MHz, CDCl.sub.3) 0.88 (t, 6H), 1.26 (m, 28H), 2.30 (m, 1H), 2.03 (s, 1H).

##STR00154##

[0109] To EtOH (40.0 mL) was added compound 6 (4.2 g, 23.0 mmol, 1.0 eq), AgSO.sub.4 (10.0 g, 32.1 mmol, 1.4 eq) and I.sub.2 (8.2 g, 32.1 mmol, 1.4 eq). The mixture was stirred at room temperature for 18 hrs. Filtered off solid. Washed with EA. The filtrate was concentrated. The residue was separated through a column to afford compound 7 5.4 g (77%) as a dark yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.

[0110] Scale up: To EtOH (1000.0 mL) was added compound 6 (100.0 g, 547.6 mmol, 1.0 eq), AgSO.sub.4 (238.0 g, 764.3 mmol, 1.4 eq) and I.sub.2 (195.2 g, 764.3 mmol, 1.4 eq). The mixture was stirred at room temperature for 18 hrs. Filtered off solid. Washed with EA (200 mL2). The filtrate was concentrated till volume. The solid was filtered and washed by cold EtOH (100 mL2) to provide compound 7 43 g as dark yellow solid with less than 5% starting material 6 inside. The filtrate was concentrated and repeated the above procedure with 0.7 eq of AgSO.sub.4 and I.sub.2. The same working up process was applied to provided second batch of compound 7 30 g as dark yellow solid with less than 5% starting material 6 inside. Combined solids to afford compound 7 73 g (43.4%). .sup.1H NMR (300 MHz, CDCl.sub.3) not available. Reaction was tracked by TLC.

##STR00155##

[0111] To anhydrous THF (10.0 mL) and TEA (10.0 mL) was added compound 4 (7.4 g, 21.2 mmol, 1.2 eq), compound 7 (5.2 g, 16.7 mmol, 1.0 eq), Pd(dppf)Cl.sub.2 (0.05 g, 0.08 mmol, 0.02 eq), CuI (0.02 g, 0.1 mmol, 0.04 eq). The mixture was degassed under vacuum and purged with N.sub.2 three times. The reaction was stirred at 70 C. for 8.0 hrs. The mixture was cooled down and EA (10 mL) was added to dilute. Filtered off the solid and concentrated the filtrate, separated with a column to afford compound 5 7.5 g (84%) as a yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3) 7.99 (s, 2H), 2.45 (m, 1H), 1.26-1.55 (m, 40H), 0.87 (t, 6H).

##STR00156##

[0112] To EtOH (20.0 mL) was added compound 5 (7.5 g, 14.1 mmol, 1.0 eq) and ammonium sulfide (8.6 g 20% water solution, 28.2 mmol, 2.0 eq). The mixture was stirred at 80 C. for 1 hr. Refilled 2.0 eq ammonium sulfide. Kept stirring at 80 C. for 1 hr. The mixture was concentrated, diluted with EA, washed with water and brine. The organic phase was collected, concentrated and separated through a column to give product 8 6.1 g (87%) as a dark red solid. .sup.1H NMR (300 MHz, CDCl.sub.3) 7.81 (s, 1H), 6.94 (s, 1H), 2.45 (m, 1H), 1.26-1.46 (m, 40H), 0.87 (t, 6H).

##STR00157##

[0113] To a 25 mL flask was added compound 8 (5.1 g, 10.2 mmol, 2.2 eq), PDA (1.7 g, 4.6 mmol, 1 eq) and imidazole (21 g, 324.5 mmol, 70 eq). The mixture was degassed under vacuum and purged with N.sub.2 three times. The reaction was stirred at 130 C. for 3 hours and 180 C. for 12 more hrs. The dark purple mixture was cooled down. The solid was washed with water (360 mL) and EtOH (360 mL), vacuum dried to give product 9 6.2 g (100%) as a dark purple solid. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.

[0114] 8.0 g of 9 and 16 mL of (cyclohexa-1,5-dien-1-yloxy)trimethylsilane were added to a two-neck round bottom flask under nitrogen. The resultant mixture was heated to 120 C in the sealed flask for 20 hrs. The reaction mixture was cooled to room temperature, dissolved in 100 mL DCM, and added to MeOH (500 mL). The precipitated solid material was filtered and washed with MeOH for 2 times to yield 6.5 g product (9 derivative).

##STR00158##

[0115] To the solution of 9 intermediate (1.5 g) in THF (100 mL), were added 20 mL isopropanol and 0.7 mL (NH4)2S solution (20 wt % in water). The resulting mixture was sealed in the flask and heated to 70 C for 2 hrs. The reaction mixture was concentrated by evaporating the solvent and re-taken into dichloromethane; the solution was washed with water for 3 times. After the solvent evaporated, the crude product was purified by silica column chromatography to yield 1.2 g product.

##STR00159##

[0116] The final step in Example 4 partially reduces the intermediate such that the product has a desired nitra-amina-amidine combination. This diamina D-nitro has a favorable combination of donor and acceptor groups on a stackable rylene fragment to achieve hyper-polarizability.

[0117] Aspects of the present disclosure provide compounds characterized by highly nonlinear electric polarizabilitly. Such compounds are useful as high dielectric constant metadielectrics for meta-capacitors with extremely high capacitance and extremely high energy storage capacity.

[0118] While the above is 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.