Long-lived redox-active molecules with low redox potential

Patent metadata

Field	Value
Publication number	US-2025118786-A1
Application number	US-202218684449-A
Country	US
Kind code	A1
Filing date	Aug 19, 2022
Priority date	Aug 19, 2021
Publication date	Apr 10, 2025
Grant date	—

Abstract

The invention provides flow batteries and methods of using flow batteries including long-lived redox-active molecules with low redox potential.

First claim

What is claimed is:

1 . A compound of formula (I):

or an ion, salt, or hydroquinone thereof, where at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is —N(R b ) 2 or —N(R c ) 2 wherein each R b is independently an optionally substituted C 1-6 alkyl and each R c is independently H or an optionally substituted C 1-6 alkyl, provided that when one R c is H, the other R c bound to the same N is an optionally substituted C 1-6 alkyl that is not CH 2 CH 2 C(═O)OH; wherein at least one R b or R c is an optionally substituted C 1-6 alkyl comprising a —S(═O) 2 R a ; —S(═O) 2 OR a ; —OS(═O) 2 OR a ; —P(═O)R a2 ; or P(═O)(OR a ) 2 substituent or is an optionally substituted C 2-6 alkyl comprising a —C(═O)OR a substituent; and each remaining of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is independently selected from H; halo; optionally substituted C 1-6 alkyl; oxo; optionally substituted C 3-10 carbocyclyl; optionally substituted C 1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C 6-20 aryl; optionally substituted C 1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; —CN; —NO 2 ; —OR a ; —SR a ; —N(R a ) 2 ; —C(═O)R a ; —C(═O)OR a ; —S(═O) 2 R a ; —S(═O) 2 OR a ; —OS(═O) 2 OR a ; —P(═O)R a2 ; and —P(═O)(OR a ) 2 ; or any two adjacent groups selected from R 8 , R 7 , R 6 , and R 5 are joined to form an optionally substituted 3-6 membered ring, wherein each R a is independently H; optionally substituted C 1-6 alkyl; optionally substituted C 3-10 carbocyclyl; optionally substituted C 1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C 6-20 aryl; optionally substituted C 1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; an oxygen protecting group; or a nitrogen protecting group.

2 . The compound of claim 1 , wherein any two or three of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are —N(R b ) 2 .

3 . The compound of claim 1 or 2 , wherein each R b is independently selected from a C 1-6 alkyl group substituted with S(═O) 2 OH, OS(═O) 2 OH, or C(═O)OH, such as —CH 2 S(═O) 2 OH, —CH 2 CH 2 S(═O) 2 OH, —CH 2 CH 2 CH 2 CH 2 S(═O) 2 OH, —CH 2 CH 2 CH 2 CH 2 CH 2 S(═O) 2 OH, —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 S(═O) 2 OH, —CH(CH 3 )OS(═O) 2 OH, —CH 2 CH(CH 3 )OS(═O) 2 OH, —CH 2 CH 2 CH(CH 3 )OS(═O) 2 OH, —CH 2 CH 2 CH 2 CH(CH 3 )OS(═O) 2 OH, —CH 2 CH 2 CH 2 CH 2 CH(CH 3 )OS(═O) 2 OH, —CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )OS(═O) 2 OH, —CH 2 OS(═O) 2 OH, —CH 2 CH 2 OS(═O) 2 OH, —CH 2 CH 2 CH 2 OS(═O) 2 OH, —CH 2 CH 2 CH 2 CH 2 OS(═O) 2 OH, —CH 2 CH 2 CH 2 CH 2 CH 2 OS(═O) 2 OH, —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 OS(═O) 2 OH, —C(═O)OH, —CH 2 C(═O)OH, —CH 2 CH 2 C(═O)OH, —CH 2 CH 2 CH 2 C(═O)OH, —CH 2 CH 2 CH 2 CH 2 C(═O)OH, or —CH 2 CH 2 CH 2 CH 2 CH 2 C(═O)OH, or a salt or ion thereof.

4 . The compound of any one of claims 1-3 , wherein the C 1-6 alkyl group is a C 3-6 alkyl group.

5 . The compound of claim 1 or 2 , wherein the compound of formula (I) is:

or an ion, salt, or hydroquinone thereof.

6 . The compound of claim 1 , wherein the compound of formula (I) is produced by reacting 2,6-diaminoanthraquinone or 2,7-diaminoanthraquinone with 1,3-propanesultone, 1,3,2-dioxathiolane 2,2-dioxide, 3-methyl-1,2-oxathiolane 2,2-dioxide, or γ-butyrolactone.

7 . The compound of claim 1 , wherein the compound of formula (I) is produced by reacting 2,6-diaminoanthraquinone or 2,7-diaminoanthraquinone with a mixture of at least two of 1,3-propanesultone, 1,3,2-dioxathiolane 2,2-dioxide, or 3-methyl-1,2-oxathiolane 2,2-dioxide.

8 . The compound of any one of claims 1-7 , wherein the compound of formula (I) is a salt comprising a lithium cation, a potassium cation, a cesium cation, or an organic cation.

9 . A method of producing a compound of formula (I), comprising reacting an aminoanthraquinone with 1,3-propanesultone, 1,3,2-dioxathiolane 2,2-dioxide, 3-methyl-1,2-oxathiolane 2,2-dioxide, γ-butyrolactone, or a combination thereof.

10 . The method of claim 9 , wherein the aminoanthraquinone is 2,6-diaminoanthraquinone or 2,7-diaminoanthraquinone.

11 . A battery comprising first and second electrodes, wherein the first electrode is in contact with a posolyte and/or the second electrode is in contact with a negolyte, wherein the posolyte and/or negolyte comprises a compound of formula (I).

12 . The battery of claim 11 , further comprising a positive and a negative redox active species, and the compound of formula (I) is a redox mediator.

13 . The battery of claim 11 , wherein the battery is a redox flow battery or a redox targeting battery.

14 . The battery of claim 13 , wherein the redox flow battery comprises a redox active species which is or comprises bromine, chlorine, iodine, molecular oxygen, vanadium, chromium, cobalt, iron, aluminum, manganese, cobalt, nickel, copper, or lead.

15 . A method of storing energy by oxidizing and/or reducing a compound of formula (I):

or an ion, salt, or hydroquinone thereof, where at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is —N(R b ) 2 or —N(R c ) 2 wherein each R b is independently an optionally substituted C 1-6 alkyl and each R c is independently H or an optionally substituted C 1-6 alkyl, provided that when one R c is H, the other R c bound to the same N is an optionally substituted C 1-6 alkyl that is not CH 2 CH 2 C(═O)OH; and each remaining of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is independently selected from H; halo; optionally substituted C 1-6 alkyl; oxo; optionally substituted C 3-10 carbocyclyl; optionally substituted C 1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C 6-20 aryl; optionally substituted C 1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; —CN; —NO 2 ; —OR a ; —SR a ; —N(R a ) 2 ; —C(═O)R a ; —C(═O)OR a ; —S(═O) 2 R a ; —S(═O) 2 OR a ; —OS(═O) 2 OR a ; —P(═O)R a2 ; and —P(═O)(OR a ) 2 ; or any two adjacent groups selected from R 8 , R 7 , R 6 , and R 5 are joined to form an optionally substituted 3-6 membered ring, wherein each R a is independently H; optionally substituted C 1-6 alkyl; optionally substituted C 3-10 carbocyclyl; optionally substituted C 1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C 6-20 aryl; optionally substituted C 1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; an oxygen protecting group; or a nitrogen protecting group.

16 . The method of claim 15 , wherein the compound of formula (I) is a negolyte of a redox flow battery.

17 . The method of claim 16 , wherein the compound of formula (I) is a redox mediator.

Assignees

• Harvard College

Inventors

• Wu Min
• Gordon Roy G
• Aziz Michael J

Classifications

• C07C309/14 Primary

  containing amino groups bound to the carbon skeleton · CPC title

• C07C229/18

  the nitrogen atom of the amino group being further bound to carbon atoms of six-membered aromatic rings · CPC title

• H01M8/188 Primary

  by recharging of redox couples containing fluids; Redox flow type batteries · CPC title

• C07C305/06

  Hydrogenosulfates · CPC title

• Y02E60/50

  Fuel cells · CPC title