Organic compound, crystal dielectric layer and capacitor

Abstract

The present disclosure provides an organic compound characterized by electronic polarizability and having a following general structural formula: ##STR00001## where Core is an aromatic polycyclic conjugated molecule, R.sub.1 is group providing solubility of the organic compound in an organic solvent, n is 1, 2, 3, 4, 5, 6, 7 or 8, R.sub.2 is substitute located in apex positions, R3 and R4 are substitutes located in side (lateral) positions and, the core has flat anisometric form and the R.sub.2 substitutes are selected from hydrogen and electrophilic groups (acceptors) and R.sub.3 substitutes and R.sub.4 substitutes are independently selected from hydrogen and nucleophilic groups (donors) or vice versa R.sub.3 substitutes and R.sub.4 substitutes are independently selected from hydrogen and nucleophilic groups (donors) and R.sub.2 substitutes are selected from hydrogen and electrophilic groups (acceptors), and the substitutes R.sub.2, R.sub.3 and R.sub.4 cannot all be hydrogen.

Claims

1. An organic compound characterized by electronic polarizability and having a following general structural formula: ##STR00077## where Core is an aromatic polycyclic conjugated molecule, R.sub.1 is independently 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, fluorinated alkyl, chlorinated alkyl, branched and complex alkyl, branched and complex fluorinated alkyl, branched and complex chlorinated alkyl groups, and any combination thereof, n is 1, 2, 3, 4, 5, 6, 7 or 8, R.sub.2 are substitutes located in apex positions, R3 and R4 are substitutes located in side (lateral) positions, and wherein the core has flat anisometric form and the R.sub.2 substitutes are selected from hydrogen and electrophilic groups (acceptors) and R.sub.3 substitutes and R.sub.4 substitutes are independently selected from hydrogen and nucleophilic groups (donors) or vice versa R.sub.3 substitutes and R.sub.4 substitutes are independently selected from hydrogen and nucleophilic groups (donors), wherein the substitutes R.sub.2, R.sub.3 and R.sub.4 cannot all be hydrogen, and wherein the aromatic polycyclic core is comprised of rylene fragments selected from the structures 1 to 21: ##STR00078## ##STR00079## ##STR00080##

2. An organic compound according to claim 1, wherein said R.sub.1 groups are isolating groups and are attached to the aromatic polycyclic conjugated core in apex positions and/or side position.

3. An organic compound according to claim 1, 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, and phenyl (+substituted phenyl).

4. An organic compound according to claim 1, 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 (CH.sub.2CHCH.sub.2), benzyl (CH.sub.2C.sub.6H.sub.5) groups, and phenyl (+substituted phenyl).

5. An organic compound according to claim 1, wherein amino groups (NH.sub.2) are used as donors and nitro groups are used as acceptors.

6. A crystal dielectric layer comprising the organic compound according to any of claims 1-2, 3-4, 5.

7. A capacitor comprising a first electrode, a second electrode, and a crystal dielectric layer disposed between said first and second electrodes, wherein said crystal dielectric layer comprises the organic compound according to any of claims 1-2, 3-4, 5, and wherein said crystal dielectric layer comprises supramolecules formed with the aromatic polycyclic conjugated cores, and isotropic insulating sublayers formed with the R.sub.1 groups served as the isolating groups.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1 schematically shows a capacitor according to an aspect of the present disclosure.

DETAILED DESCRIPTION

(2) While various implementations of aspects of the present disclosure have been shown and described herein, it will be obvious to those skilled in the art that such implementations are provided by way of example only. Numerous variations, changes, and substitutions may occur to those skilled in the art without departing from the aspects of the present disclosure. It should be understood that various alternatives to the implementations described herein may be employed.

(3) The present disclosure provides an organic compound. Existence of the electrophilic groups (acceptors) and the nucleophilic groups (donors) in the aromatic polycyclic conjugated core promotes increase of electronic polarizability of these cores. Under the influence of an 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 core is non-uniform.

(4) In one implementation, the R.sub.1 groups serve as the isolating groups and are attached to the aromatic polycyclic conjugated core in apex positions and/or side position. In another embodiment of the present invention, the aromatic polycyclic conjugated Core in the above general structural formula comprises rylene fragments. In still another embodiment of the present invention, the rylene fragments are selected from structures 1-21 as given in Table 1.

(5) TABLE-US-00001 TABLE 1 Examples of the polycyclic organic compound comprising rylene fragments 1 2 3 4 5 6 7 0 8 9 10 11 12 13 14 15 16 17 0 18 19 20 21
In another implementation of the organic compound, the aromatic polycyclic conjugated Core in the above general structural formula comprises an electro-conductive oligomer including a phenylene oligomer and a polyacene quinine radical oligomer. In still another embodiment of the present invention, the electro-conductive oligomer is selected from the structures 22 to 30 as given in Table 2 wherein I=2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, Z is O, S or NR.sub.1, and R.sub.1 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.

(6) TABLE-US-00002 TABLE 2 Examples of the polycyclic organic compound comprising electro- conductive oligomer 22 23 24 25 26 27 0 28 29 30

(7) In yet another implementation, the aforementioned electrophilic groups (acceptors) in the above general structural formula 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.

(8) In still another implementation, the aforementioned nucleophilic groups (donors) in the above general structural formula 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 (CH.sub.2CHCH.sub.2), benzyl (CH.sub.2C.sub.6H.sub.5) groups, phenyl (+substituted phenyl) and other aryl (aromatic) groups. In one implementation, the organic solvent is selected from benzene, toluene, xylenes, acetone, acetic acid, methylethylketone, hydrocarbons, chloroform, carbontetrachloride, methylenechloride, dichlorethane, chlorobenzene, alcohols, nitromethan, acetonitrile, dimethylforamide, 1,4-dioxane, tetrahydrofuran (THF), methylcyclohexane (MCH), and any combination thereof. In another implementation, the groups providing solubility of the organic compound are independently selected from 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, butyl, I-butyl and t-butyl groups, and the aryl group is selected from phenyl, benzyl and naphthyl groups.

(9) In yet another implemenation, the aromatic polycyclic conjugated Core in the above general structural formula comprises rylene fragment, the amino groups (NH.sub.2) are used as donors, nitro groups are used as acceptors and said organic compound formulas are selected from structures 31 to 36 as shown in Table 3.

(10) TABLE-US-00003 TABLE 3 Examples of the organic compound 31 32 33 34 35 36

(11) In yet another implementation, the aromatic polycyclic conjugated Core in the above general structural formula comprises rylene fragment and selected from structures 37-39 as shown in Table 4, where other ring position of R.sub.1 and R.sub.2 are possible so that trans and cis isomers are possible.

(12) TABLE-US-00004 TABLE 4 Examples of the organic compound 37 0 38 39
In still another embodiment of the present invention, the aromatic polycyclic conjugated Core in the above general structural formula comprises rylene fragment and has a structure selected from structures 40-43 as shown in Table 5.

(13) TABLE-US-00005 TABLE 5 Examples of the organic compound 40 41 42 43 44 45 46

(14) In an aspect, the present disclosure provides a crystal dielectric layer comprising the disclosed organic compound. The crystal dielectric layers are produced from the disclosed organic compound by Cascade Crystallization. The symmetric arrangement of electrophilic groups (acceptors) and nucleophilic groups (donors) in the aromatic polycyclic conjugated core promotes formation of supramolecules.

(15) Cascade Crystallization process involves a chemical modification step and four steps of ordering during the crystal dielectric 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 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.

(16) The Cascade Crystallization process is used for production of thin crystalline dielectric 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 in the direction of one of the optical axes.

(17) In another aspect, the present disclosure provides a capacitor, an example of which is shown in FIG. 1. The capacitor generally includes a first electrode (1), a second electrode (2), and a crystal dielectric layer (3) disposed between said first and second electrodes and wherein said crystal dielectric layer comprises sublayers (4) which are characterized by electronic polarizability and have supramolecules formed with the aromatic polycyclic conjugated Cores, of any of the types described herein, and isotropic insulating sublayers (5) formed with the A-groups which serve as the isolating groups described above. These insulating sublayers prevent occurrence of percolation with formation of continuous electrically conductive channels under action of electric field.

(18) 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, e.g., they may 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, 2 which may correspond to the thickness of the crystal dielectric layer 106 may range from about 1 m to about 10 000 m. As noted in Equation (2) above, the maximum voltage V.sub.bd between the electrodes 102, 103 is approximately the product of the breakdown field and the electrode spacing d. For example, if, E.sub.bd=0.1 V/nm and the spacing d between the electrodes 1, 2 is 10,000 microns (100,000 nm), the maximum voltage V.sub.bd would be 100,000 volts.

(19) The electrodes 1, 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 102,104 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 are manufacturable with roll-to-roll processes similar to those used to manufacture magnetic tape or photographic film.

(20) 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.

(21) 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.oA/d,(3)
where .sub.o 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=CV.sub.bd.sup.2(4)
which may be rewritten using equations (2) and (3) as:
U=.sub.oAE.sub.bd.sup.2d(5)

(22) 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 210.sup.16 Joules.

(23) For a dielectric constant 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.

(24) In order that aspects of the present disclosure 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 be limiting the scope.

EXAMPLE 1

(25) This Example describes synthesis of the disclosed organic compound (see, general structural formula 40 in Table 5) according following structural scheme:

(26) ##STR00049## ##STR00050##

(27) N,N-Didodecyl-4-Acetamidobenzenesulfonamine: N-acetylsulfanilyl chloride (3.3 g, 14.12 mmol) and didodecylamine (4.77 g, 13.48 mmol) were added to a 100 mL flask sealed with a rubber septa under nitrogen. The flask was cooled on an ice bath, and pyridine (18 mL) cooled on an ice bath was added to the chloride amine flask via syringe. The flask was placed in the refrigerator overnight.

(28) The mixture was diluted with ethyl acetate (150 mL) and filtered into a separatory funnel (note, starting didodecylamine is poorly soluble so most unreacted amine is removed at this step). The organic layer was washed 3 with water, 3 dilute HCl, 1 sat. NaHCO.sub.3, 1 brine, dried over MgSO.sub.4, and then filtered through a silica gel pad, rinsing with 50 mL ethyl acetate. The solvent was removed under reduced pressure, and recrystallized in hexane (by storing in a refrigerator for several hours). The solid was filtered, rinsed with cold hexanes, and allowed to dry with hood airflow. 2.95 g of off white crystals recovered, 40% yield.

(29) 4-Amino N,N-didodecylbenzenesulfonamine: A 100 mL flask was charged with N,N-Didodecyl-4-Acetamidobenzenesulfonamine (2.0 g, 3.63 mmol), to which was added a solution of KOH (2.037 g, 36.3 mmol) dissolved in water (2 ml), methanol (10 mL) and THF (10 mL). The solution was heated to reflux for 4 hours. Reaction was complete by tlc (100% EtAc). Cooled to RT, extracted 350 mL hexanes, 125 mL EtAc, washed the combined organic layers with water, and then brine, dried over MgSO.sub.4, and filtered through silica gel pad, rising with EtAc (50 mL). Dried over reduced pressure and recovered 1.82 g of beige solid (99% yield).

(30) General Structural Formula 40 in Table 5: (Re: Robb and Hawker, J. Org. Chem. 2014, 79, 6360-6365, which is incorporated herein by reference) A 2 necked 50 mL flask was charged with 4-Amino N,N-didodecylbenzenesulfonamine (1.7 g, 3.35 mmol), and powdered mixture of perylene-3,4,9,10-tetracarboxylic dianhydride (0.657 g, 1.675 mmol) and imidazole (7 g). The flask was purged with N.sub.2 for 10 minutes, and then placed in an oil bath (130 C) with stirring for 20 hrs (tlc shows absence of starting amine). The cooled mixture was dissolved in methylene chloride, washed with 1M HCl, the aqueous layer being further washed 3 methylene chloride, adding a minimum amount of IPA to reduce the emulsion. The following procedures are in summary carried out: drying of the organic layer over MgSO.sub.4, filtering of through a 1 silica gel pad, rinsing with of 10% of methanol/CH.sub.2C.sub.12, and removing the solvent under reduced pressure. Recovered weight (mass) was equal to 2 g (85%).

EXAMPLE 2

(31) This Example describes synthesis of the disclosed organic compound (see, general structural formula 41 in Table 5) according following structural scheme:

(32) ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055##

(33) To a cooled (ice-water) concentrated H.sub.2SO.sub.4 (240.0 mL) was added sulfonyl chloride 1 (50.0 g, 0.21 mol, 1.0 ea) in portions. The mixture was stirred at 0 C. until a clear solution. A pre-mixed mixture of concentrated H.sub.2SO.sub.4 (98%, 30.0 mL) and concentrated HNO.sub.3 (70%, 30.0 mL) was added slowly to maintain reaction temperature below 10 C. After addition, the reaction mixture was stirred at 10 C. for 4.0 hrs, poured into ice-water (2000 mL). The precipitate was brought into hot benzene (60 C., 1000 mL), separated organic layer from water, dried over Na.sub.2SO.sub.4, filtered and concentrated to give 47.0 g (77%) of a mixture mono-nitro compound 2 and bis-nitro 3 (2:3=3:2 by NMR). .sup.1H NMR (300 MHz, CDCl.sub.3) 10.67 (bs, 1H), 9.19-9.16 (d, J=9.0 Hz, 1H), 9.12 (s, 1H), 9.04 (bs, 2H), 8.918.90(d, J=3.0 Hz, 1H), 8.26-8.22 (dd, J=9.0 Hz, J=3.0 Hz, 1H), 2.38 (s, 3H).

(34) To a solution of didodecylamine (25.0 g, 70.7 mmol, eq) in dichloromethane (400 mL), was added pyridine (35.1 g, 440.0 mmol, 5.0 eq) and a mixture of mono-nitro 2 and bis-nitro 3 (20.0 g, 68.9 mmol, 1.0 eq) at 0 C. The resulting mixture was stirred at room temperature for 16 hrs, diluted with dichloromethane (400 mL), washed with water (2200 mL), brine (200 mL), dried over dried over Na.sub.2SO.sub.4, filtered and concentrated to give a residue. The crude product was purified by flash chromatography column (EtOAc/Hexane=3/10 to 1/2) to give 6.3 g (15.4%) of mono-nitro compound 4 as a yellow solid and 11.0 g (26.7%) of bis-nitro 5 as a red-yellow solid. Compound 4: .sup.1H NMR (300 MHz, CDCl.sub.3) 10.50 (bs, 1H), 8.998.96 (d, J=9.0 Hz, 1H), 8.64 (s, 1H), 8.02-8.98 (d, J=10.8 Hz, 1H), 3.163.11 (t, J=7.8 Hz, 4H), 2.34 (s, 3H), 1.611.44 (m. 4H), 1.401.15 (m, 36H), 1.000.80 (t, J=6.0 Hz, 6H).

(35) To a suspension of the mono-nitro compound 4 (6.3 g, 10.6 mmol, 1.0 eq) in ethanol (700 mL) was added Pd/C (10% on carbon, 50% wet, 1.3 g, 10 w %). The mixture was degassed (vacuum and fill with H.sub.2) three times, and stirred at room temperature under 1 atm H.sub.2 for 16 hrs, filtered through a pad of Celite. The filtrate was concentrated to give 6.0 g (100%) of the amine 6 as a yellow solid. .sup.1H.Math.NMR.Math.(300.Math.MHz, CDCl.sub.3) 7.417.38 (d, J=8.1 Hz, 1H), 7.32 (bs, 1H), 7.20 (s, 1H), 7.187.15 (dd, J=8.4 Hz, J=1.8 Hz, 1H), 3.95 (bs, 2H), 3.08-3.03 (t, J=7.5 Hz, 4H), 1.451.40 (m, 4H), 1.351.15 (m, 36H), 0.920.80 (t, J=6.3 Hz, 6H).

(36) To a solution of the amine 6 (6.0 g, 10.6 mmol, 1.0 eq) in THF (30 mL) and MeOH (30 mL) was added a solution of KOH (6.0 g, 110.0 mmol, 10.0 eq) in water (5.0 mL). The mixture was stirred at reflux for 6 hrs and concentrated. The residue was partitioned between EtOAc (100 mL) and water (100 mL). Organic layer was separated, dried over Na.sub.2SO.sub.4, filtered and concentrated to give a residue. The crude product was purified by flash chromatography column (EtOAc/Hexane=1/1) to give 3.5 g (63.1%) of diamine 7 as a light yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3) 7.187.14 (dd, J=7.8 Hz, J=1.8 Hz, 1H), 7.12 (s, 1H), 6.726.69 (d, J=8.1 Hz, 1H), 3.073.02 (t, J=7.2 Hz, 4H), 1.451.40 (m, 4H), 1.351.15 (m, 36H), 1.000.80 (t, J=6.0 Hz, 6H).

(37) The diamine 7 (3.4 g, 6.5 mmol, 2.2 equ), 3,4,9,10-perylenetetracarboxylic dianhydride (1.2 g, 2.9 mmol, 1.0 eq) and imidazole (31.0 g, 455.0 mmol, 70 eq to diamine) were mixed well in a 200 mL round-bottom flask equipped with a rotavap bump guard. The mixture was degased (vacuum and fill with N.sub.2) three times and stirred at 145 C. for 3 hrs, 180 C. for 12 hrs. After cooling to rt, the reaction mixture was crushed into water (500 mL), stirred for 1 hour, and filtered through a filter paper to collected precipitate which was washed with water (450 mL) and ethanol (450 mL), dried on a high vacuum to give 3.7 g (91.5%) of the diamidine 8 as a dark purple solid. .sup.1H NMR (300 MHz, CDCl.sub.3) 8.808.40 (m, 8H), 8.228.06 (m, 2H), 7.70-7.60 (m, 4H), 3.203.00 (m, 8H), 1.601.40 (m, 8H), 1.401.10 (m, 72H), 0.960.80 (m, 12H).

EXAMPLE 3

(38) This example describes synthesis of the disclosed organic compound (see, general structural formula 42 in Table 5) according following structural scheme:

(39) ##STR00056## ##STR00057## ##STR00058## ##STR00059##

(40) Sulfonyl chloride 1 (50.0 g, 0.21 mol, 1.0 ea) was added in portions to cooled (ice-water) concentrated H.sub.2SO.sub.4 (240.0 mL). The mixture was stirred at 0 C. until a clear solution. A pre-mixed mixture of concentrated H.sub.2SO.sub.4 (98%, 30.0 mL) and concentrated HNO.sub.3 (70%, 30.0 mL) was added slowly to maintain reaction temperature below 10 C. After addition, the reaction mixture was stirred at 10 C. for 4.0 hrs, poured into ice-water (2000 mL). The precipitate was brought into hot benzene (60 C., 1000 mL), separated organic layer from water, dried over Na.sub.2SO.sub.4, filtered and concentrated to give 47.0 g (77%) of a mixture mono-nitro compound 2 and bis-nitro compound 3 (2:3=3:2 by NMR). .sup.1H NMR (300 MHz, CDCl.sub.3) 10.67 (bs, 1H), 9.199.16 (d, J=9.0 Hz, 1H), 9.12 (s, 1H), 9.04 (bs, 2H), 8.918.90 (d, J=3.0 Hz, 1H), 8.268.22 (dd, J=9.0 Hz, J=3.0 Hz, 1H), 2.38 (s, 3H).

(41) To a solution of didodecylamine (25.0 g, 70.7 mmol, eq) in dichloromethane (400 mL), was added pyridine (35.1 g, 440.0 mmol, 5.0 eq) and a mixture of mono-nitro 2 and bis-nitro 3 (20.0 g, 68.9 mmol, 1.0 eq) at 0 C. The resulting mixture was stirred at room temperature for 16 hrs, diluted with dichloromethane (400 mL), washed with water (2200 mL), brine (200 mL), dried over dried over Na.sub.2SO.sub.4, filtered and concentrated to give a residue. The crude product was purified by flash chromatography column (EtOAc/Hexane=3/10 to 1/2) to give 6.3 g (15.4%) of mono-nitro compound 4 as a yellow solid and 11.0 g (26.7%) of bis-nitro 5 as a red-yellow solid. 5: .sup.1H NMR (300 MHz, CDCl.sub.3) 8.89 (s, 2H), 8.76 (bs, 2H), 3.183.13 (t, J=7.5 Hz, 4H), 2.34 (s, 3H), 1.611.44 (m, 4H), 1.401.15 (m, 36H), 0.900.80 (t, J=6.3 Hz, 6H).

(42) To a solution of the bis-nitro compound 5 (8.6 g, 14.4 mmol, 1.0 eq) in ethanol (800 mL) and cyclohexane (800 mL) was added Pd/C (10% on carbon, 50% wet, 0.9 g, 5 w %). The mixture was degassed (vacuum and fill with H.sub.2) three times, and stirred at room temperature under 1 atm H.sub.2 for 1 hour, filtered through a Celite. The filtrate was concentrated to give 4.5 g (55.0%) of the diamine 9 as a yellow-red solid, and 2.3 g of a intermediate as a yellow solid which was hydrogenated again following the above procedure to give 1.3 g (16.8%) of the triamine 10 as a dark-brown solid. Compound 9: .sup.1H NMR (300 MHz, CDCl.sub.3) 8.18 (s, 1H), 7.28 (s, 1H), 6.38 (s, 2H), 3.62 (s, 2H), 3.123.06 (t, J=8.6 Hz, 4H), 1.60-1.45 (m, 4H), 1.381.15 (m, 36H), 0.920.82 (t, J=6.3 Hz, 6H).

(43) Mixed well the diamine 9 (4.5 g, 7.9 mmol, 2.2 equ), 3,4,9,10-perylenetetracarboxylic dianhydride (1.4 g, 3.6 mmol, 1.0 eq) and imidazole (38.0 g, 550.0 mmol, 70 eq to diamine) into a 200 mL round-bottom flask equipped with a rotavap bump guard. The mixture was degased (vacuum and fill with N.sub.2) three times and stirred at 145 C. for 3 hrs, 180 C. for 12 hrs. After cooling to rt, the reaction mixture was crushed into water (600 mL), stirred for 1 hour, and filtered through a filter paper to collected precipitate which was washed with water (450 mL) and ethanol (450 mL), dried on a high vacuum to give 5.2 g (99.0%) of the diamidine 11 as a dark purple solid.

EXAMPLE 4

(44) This example describes synthesis of the disclosed organic compound (see, general structural formula 43 in Table 5) according following structural scheme:

(45) ##STR00060## ##STR00061## ##STR00062## ##STR00063##

(46) To a cold (ice-water) con. H.sub.2SO.sub.4 (240.0 mL) was added sulfonyl chloride 1 (50.0 g, 0.21 mol, 1.0 ea) in portions. The mixture was stirred at 0 C. until a clear solution. A pre-mixed mixture of concentrated H.sub.2SO.sub.4 (98%, 30.0 mL) and concentrated HNO.sub.3 (70%, 30.0 mL) was added slowly to maintain reaction temperature below 10 C. After addition, the reaction mixture was stirred at 10 C. for 4.0 hrs, poured into ice-water (2000 mL). The precipitate was brought into hot benzene (60 C., 1000 mL), separated organic layer from water, dried over Na.sub.2SO.sub.4, filtered and concentrated to give 47.0 g (77%) of a mixture mono-nitro compound 2 and bis-nitro compound 3 (2:3=3:2 by NMR). .sup.1H NMR (300 MHz, CDCl.sub.3) 10.67 (bs, 1H), 9.199.16 (d, J=9.0 Hz, 1H), 9.12 (s, 1H), 9.04 (bs, 2H), 8.918.90 (d,J=3.0 Hz, 1H), 8.268.22 (dd, J=9.0 Hz,J=3.0 Hz, 1H), 2.38 (s, 3H).

(47) To a solution of didodecylamine (25.0 g, 70.7 mmol, eq) in dichloromethane (400 mL), was added pyridine (35.1 g, 440.0 mmol, 5.0 eq) and a mixture of mono-nitro 2 and bis-nitro 3 (20.0 g, 68.9 mmol, 1.0 eq) at 0 C. The resulting mixture was stirred at room temperature for 16 hrs, diluted with dichloromethane (400 mL), washed with water (2200 mL), brine (200 mL), dried over dried over Na.sub.2SO.sub.4, filtered and concentrated to give a residue. The crude product was purified by flash chromatography column (EtOAc/Hexane=3/10 to 1/2) to give 6.3 g (15.4%) of mono-nitro compound 4 as a yellow solid and 11.0 g (26.7%) of bis-nitro 5 as a red-yellow solid. 5: .sup.1H NMR (300 MHz, CDCl.sub.3) 8.89 (s, 2H), 8.76 (bs, 2H), 3.183.13 (t, J=7.5 Hz, 4H), 2.34 (s, 3H), 1.611.44 (m, 4H), 1.401.15 (m, 36H), 0.900.80 (t, J=6.3 Hz, 6H).

(48) To a solution of the bis-nitro compound 5 (8.6 g, 14.4 mmol, 1.0 eq) in ethanol (800 mL) and cyclohexane (800 mL) was added Pd/C (10% on carbon, 50% wet, 0.9 g, 5 w %). The mixture was degassed (vacuum and fill with H.sub.2) three times, and stirred at room temperature under 1 atm H.sub.2 for 1 hour, filtered through a Celite. The filtrate was concentrated to give 4.5 g (55.0%) of the diamine 9 as a yellow-red solid, and 2.3 g of a intermediate as a yellow solid which was hydrogenated again following the above procedure to give 1.3 g (16.8%) of the triamine 10 as a dark-brown solid. Compound 10: .sup.1H NMR (300 MHz, CDCl.sub.3) 6.77 (s, 2H), 3.553.35 (m, 6H), 3.063.00 (t, J=7.5 Hz, 4H), 1.551.42 (m, 4H), 1.381.18 (m, 36H), 0.900.86 (t, J=6.3 Hz, 6H), 2.982.94 (m, 2H), 2.682.64 (m, 2H), 2.60 (s, 3H), 2.30 (s, 3H).

(49) Mixed well the diamine 10 (0.5 g, 0.88 mmol, 2.2 equ), 3,4,9,10-perylenetetracarboxylic dianhydride (0.16 g, 0.40 mmol, 1.0 eq) and imidazole (4.2 g, 61.6 mmol, 70 eq to diamine) into a 100 mL round-bottom flask equipped with a rotavap bump guard. The mixture was degased (vacuum and fill with N.sub.2) three times and stirred at 145 C. for 3 hrs, 180 C. for 12 hrs. After cooling to rt, the reaction mixture was crushed into water (200 mL), stirred for 1 hour, and filtered through a filter paper to collected precipitate which was washed with water (430 mL) and ethanol (430 mL), dried on a high vacuum to give 0.5 g (89.5%) of the diamidine 12 as a dark solid.

EXAMPLE 5

(50) This example describes synthesis of the disclosed organic compound (see, general structural formula 44 in Table 5) according following structural schemes:

(51) ##STR00064##
To anhydrous DMF (15.0 mL) was added compound 1 (3.3 g, 15 mmol, 1.0 eq), compound 2 (4.8 mL, 18 mmol, 1.2 eq), Pd(dppf)Cl.sub.2 (0.24 g, 0.3 mmol, 0.02 eq), CuI (0.12 g, 0.6 mmol, 0.04 eq) and K.sub.2CO.sub.3 (4.2 g, 30 mmol, 2.0 eq). The mixture was degassed under vacuum and purged with N.sub.2 three times. The reaction was stirred at 90 C. for 8.0 hrs. The mixture was cooled down and EA (15 mL) was added to dilute. Filtered off the solid and poured the filtrate into water, extracted with EA (310 mL). Washed organic phase with water (10 mL) and brine (10 mL), dried over MgSO.sub.4, filtered and concentrated. The residue was treated with a sil-gel column to give 2.1 g (40%) of product 3 as a dark yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3) 8.17 (s, 1H), 7.34 (d, 1H), 6.70 (d, 1H), 6.19 (s, 2H), 2.36 (t, 2H), 1.26- 1.56 (m, 22H), 0.87 (t, 3H).

(52) ##STR00065##
To EA (2.0 mL) was added compound 3 (500.0 mg, 1.44 mmol, 1.0 eq) and Pd/C (50.0 mg, 0.1 eq). The mixture was stirred at room temperature under H.sub.2-balloon for 20 min. Filtered off solid, concentrated to give compound 4 346 mg (80%) as light yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3) 6.61 (d, 1H), 6.50 (d, 1H), 6.54 (s, 1H), 7.86 (t, 2H), 1.25 (m, 22H), 0.88 (t, 3H).

(53) ##STR00066##

(54) To a 25 mL flask was added compound 4 (758 mg, 2.4 mmol, 2.2 eq), PDA (429 mg, 1.1 mmol, 1 eq) and imidazole (5.2 g, 77 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 hrs and 180 C. for 12 more hrs. The dark purple mixture was cooled down. The solid was washed with water (32 mL) and EtOH (32 mL), vacuum dried to give product 5 912 mg (40%) as a dark purple solid. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.

Example 6

(55) This example describes synthesis of the disclosed organic compound (see, general structural formula 46 in Table 5) according following structural schemes:

(56) ##STR00067##
Compound 1 (5 g, 27.3 mmol, 1 eq) was suspended in AcOH (50 mL). Br.sub.2 (1.5 mL, 30 mmol, 1.1 eq) was added dropwise at rt. After addition, the temperature was increased to 120 C. and kept stirring at this temperature for 2 hrs. The mixture was poured into ice water. The precipitate was filtered, washed with water and dried under vacuum to give product 2 6.8 g (95%) as a yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.

(57) ##STR00068##
To anhydrous DMF (10.0 mL) was added compound 2 (2.0 g, 7.6 mmol, 1.0 eq), compound 3 (2.4 mL, 9.1 mmol, 1.2 eq), Pd(dppf)Cl.sub.2 (0.13 g, 0.15 mmol, 0.02 eq), Cut (0.06 g, 0.3 mmol, 0.04 eq) and K.sub.2CO.sub.3 (2.1 g, 15 mmol, 2.0 eq). The mixture was degassed under vacuum and purged with N.sub.2 three times. The reaction was stirred at 90 C. for 8.0 hrs. The mixture was cooled down and EA (10 mL) was added to dilute. Filtered off the solid and poured the filtrate into water, extracted with EA (35 mL). Washed organic phase with water (5 mL) and brine (5 mL), dried over MgSO.sub.4, filtered and concentrated. The residue was treated with a sil-gel column to give 520 mg (17%) of product 4 as a dark yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3) 8.53 (s, 2H), 2.37 (t, 2H), 1.26-1.55 (m,22H), 0.87 (t, 3H).

(58) ##STR00069##
To EtOH (1.0 mL) was added compound 4 (60 mg, 0.15 mmol, 1.0 ea) and ammonium sulfide (104 mg 20% water solution, 0.3 mmol, 2.0 eq). The mixture was stirred at 80 C. for 1 hr. Refilled 2.0 eq ammonium sulfide. The received mixture again was stirred at 80 C. for 1 hr. The mixture was concentrated, diluted with EA, washed with water and brine. Organic phase was collected, concentrated and separated through a column to give product 5 21.8 mg (40%) as a dark red solid. .sup.1H NMR (300 MHz, CDCl.sub.3) 7.81 (s, 1H), 6.94 (s, 1H), 6.03 (s, 2H), 3.26 (s, 2H), 2.36 (t, 2H), 1.26-1.53 (m, 22H), 0.87 (t, 3H).

(59) ##STR00070##
To a 5 mL vial was added compound 5 (21.8 mg, 0.06 mmol, 2.2 eq), PDA (10.8 mg, 0.028 mmol, 1 eq) and imidazole (131 g, 1.93 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 hrs and 180 C. for 12 more hrs. The dark purple mixture was cooled down. The solid was washed with water (30.5 mL) and EtOH (30.5 mL), vacuum dried to give product 6 27 mg (45%) as a dark purple solid. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.

EXAMPLE 6

(60) This example describes synthesis of the disclosed organic compound (see, general structural formula 46 in Table 5) according following structural schemes:

(61) ##STR00071##
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. Collected DCM phase, extracted with DCM (25 mL2), combined organic phase, washed with water and brine, dried over MgSO.sub.4 and concentrated to give compound 2 18 g (90%) as a colorless oil. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.

(62) ##STR00072##
To MeOH (60.0 mL) was added freshly made compound 2 (18 g, 51.1 mmol, 2.0 eq), bestmann reagent (5.0 g, 25.6 mmol, 1.0 eq) and K.sub.2CO.sub.3 (7.1 g, 51.1 mmol, 2.0 eq). The mixture was stirred at room temperature for 24 hrs. EA (30.0 mL) was added to dilute the mixture. Mixture was filtered to separate solid sediment (precipitate). Washed with EA. The filtrate was concentrated. The residue was separated through a column to afford compound 3 7.4 g (82%) as white solid. .sup.1H NMR (300 MHz, CDCl.sub.3) 2.15 (m, 1H), 2.03 (s, 1H), 1.26-1.41 (m, 40H), 0.87 (t, 6H).

(63) ##STR00073##
To EtOH (40.0 mL) was added compound 5 (4.2 g, 23.0 mmol, 1.0 eq), AgSO.sub.4 (10.0 g, 32.1 mmol, 1.4 eq) and 12 (8.2 g, 32.1 mmol, 1.4 eq). The mixture was stirred at room temperature for 18 hrs. Mixture was filtered to separate solid sediment (precipitate) and washed with EA. The filtrate was concentrated. The residue was separated through a column to afford compound 6 5.4 g (77%) as a dark yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.

(64) ##STR00074##
To anhydrous THF (10.0 mL) and TEA (10.0 mL) was added compound 3 (7.4 g, 21.2 mmol, 1.2 eq), compound 6 (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 4 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).

(65) ##STR00075##
To EtOH (20.0 mL) was added compound 4 (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. The received mixture again was stirred at 80 C. for 1 hr. The mixture was concentrated, diluted with EA, washed with water and brine. Organic phase was collected, concentrated and separated through a column to give product 7 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).

(66) ##STR00076##
To a 25 mL flask was added compound 7 (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 hrs and 180 C. for 12 more hrs. The dark purple mixture was cooled down. The solid was washed with water (32 mL) and EtOH (32 mL), vacuum dried to give product 8 6.2 g (100%) as a dark purple solid. .sup.1H NMR (300 MHz, CDCl.sub.3) not available.
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.