Electro-polarizable compound and capacitor

Patent metadata

Field	Value
Publication number	US-9978517-B2
Application number	US-201615090509-A
Country	US
Kind code	B2
Filing date	Apr 4, 2016
Priority date	Apr 4, 2016
Publication date	May 22, 2018
Grant date	May 22, 2018

Abstract

An electro-polarizable compound has the following general formula:

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 a dopant group connected to Core1; a number m of R1 groups is 1, 2, 3 or 4. R2 is a substituent comprising one or more ionic groups connected to Core1; a number p of ionic groups R2 is 0, 1, 2, 3 or 4. The fragment marked NLE has a nonlinear polarization effect. Core2 is an electro-conductive oligomer self-assembling by pi-pi stacking in a column-like supramolecule, a number n of such oligomers is 0, 2, or 4. R3 is a substituent comprising one or more ionic groups connected to Core2; a number s of the ionic groups R3 is 0, 1, 2, 3 or 4. R4 is a resistive substituent providing solubility of the compound in a solvent and electrically insulating the column-like supramolecules from each other. A number k of substituents R4 is 0, 1, 2, 3, 4, 5, 6, 7 or 8.

First claim

What is claimed is:

1. An electro-polarizable compound having the following general formula (I):

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 comprising one or more rylene fragments selected from structures 1 to 12:

or a tetrapirolic macro-cyclic fragment that has a general structural formula from the group comprising structures 13-19, where M denotes an atom of metal or two protons (2H):

R1 is an dopant group connected to the aromatic polycyclic conjugated molecule (Core1) selected from nucleophilic groups (donors): —NO 2 , —NH 3 + and —NR 3 + (quaternary nitrogen salts), counterion Cl − or Br − , —CHO (aldehyde), —CRO (keto group), —SO 3 H (sulfonic acids), —SO 3 R (sulfonates), SO 2 NH 2 (sulfonamides), —COOH (carboxylic acid), —COOR (esters), —COCl (carboxylic acid chlorides), —CONH 2 (amides,), —CF 3 , —CCl 3 , —CN, wherein R is radical selected from the list consisting of alkyl, allyl (—CH 2 —CH═CH 2 ), benzyl (—CH 2 C 6 H 5 ) groups, phenyl, substituted phenyl and other aryl (aromatic) groups and electrophilic groups (acceptors): —O − (phenoxides,), —NH 2 , —NHR, NR 2 , —OH, OR (ethers), —NHCOR (amides), —OCOR (esters), alkyls, —C 6 H 5 , vinyls, wherein R is radical selected from the list consisting of alkyl, allyl (—CH2-CH═CH2) benzyl (—CH2C6H5) groups, phenyl, substituted phenyl and other aryl (aromatic) groups;
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 form 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 selected from the structures 20 to 28 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 1 -C 18 alkyl, unsubstituted or substituted C 2 -C 18 alkenyl, unsubstituted or substituted C 2 -C 18 alkynyl, and unsubstituted or substituted C 4 -C 18 aryl:

n is number of the electro-conductive oligomers which is equal to 2, or 4, R3 is a substituent comprising one or more ionic groups from a class of ionic compounds that form 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 non-polar 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.

2. 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 4 ] + , [PR 4 ] + as cation and [—CO 2 ] − , [—SO 3 ] − , [—SR 5 ] − , [—PO 3 R] − , [—PR 5 ] − as anion, wherein R is selected from the list comprising H, alkyl, and fluorine.

3. The electro-polarizable compound according to claim 1 , wherein the at least one connecting group is selected from the list comprising the following structures: 29-39, where W is hydrogen (H) or an alkyl group:

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

5. The electro-polarizable compound according to claim 1 , wherein the at least one connecting group is selected from structures 40 to 45:

6. 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.

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

8. 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.

9. 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.

10. A electro-polarizable compound of claim 1 having the following general formula (II):

wherein the Core1 is rylene fragment having following structural formula:

wherein two (m is equal to 2) dopant groups —NH 2 and —NO 2 are located on rylene phenyl rings and/or apex phenyl ring positions of the Core1,
wherein the Core2 is the electro-conductive oligomer having following structural formula:

wherein I=2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, number n of the electro-conductive oligomers is equal to 0 or 2 and the two Core2's are located in apex positions of the Core1,
wherein R3 is the ionic group [—SO 3 ] − , numbers of the ionic groups R3 is equal to 2,
wherein the ionic groups are connected to the electro-conductive oligomer (Core2) via a connecting group having following structural formula:

wherein R4 is C 18 H 37 is a resistive substituent located on the terminus positions of Core2 or apex phenyl rings of Core 1.

11. A electro-polarizable compound of claim 1 having the following general formula:

wherein the Core1 is tetrapirolic macro-cyclic fragments having following structural formula:

Assignees

• Capacitor Sciences Inc

Inventors

• Lazarev Pavel Ivan
• Furuta Paul T
• Sharp Barry K
• Li Yan

Classifications

• C07D487/22

  in which the condensed system contains four or more hetero rings · CPC title

• C09B69/00

  Dyes not provided for by a single group of this subclass · CPC title

• C09B5/62

  Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series · CPC title

• C09B47/04

  Phthalocyanines {abbreviation: Pc} · CPC title

• H01G4/14 Primary

  Organic dielectrics · CPC title