IP Library › Granted Patent US 9,978,474
Granted Patent B2
US 9,978,474 · App. 15/050,136 · Granted May 22, 2018

Conductive open frameworks

Inventors: Omar M. Yaghi (Berkeley, CA); Shun Wan (Santa Monica, CA); Christian J. Doonan (Eastwood, AU); Bo Wang (Beijing, CN); Hexiang Deng (Albany, CA)
Assignee: The Regents of the University of California
H01B1/12B01J20/22B01J20/26C07D487/22C07F5/04Y02E60/324
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Quick Facts
Patent No.
US 9,978,474
App. No.
15/050,136
Granted
May 22, 2018
Kind
B2
Abstract

The disclosure relates generally to materials that comprise conductive covalent organic frameworks. The disclosure also relates to materials that are useful to store and separate gas molecules and sensors.

Claims (50)

1. A conductive covalent-organic framework (COF) comprising:

a plurality of cores, wherein each core forms at least one imine bond to at least one linking moiety; and

wherein at least one core of the plurality of cores comprises a conductive core moiety and/or wherein at least one linking moiety comprises a conductive linking moiety and wherein the core has a structure of Formula I:

wherein:

R 1 -R 4 are independently selected from the group consisting of H, D, FG, (C 1 -C 20 )alkyl, substituted (C 1 -C 20 )alkyl, (C 1 -C 20 )alkenyl, substituted (C 1 -C 20 )alkenyl, (C 1 -C 20 )alkynyl, substituted (C 1 -C 20 )alkynyl, hetero-(C 1 -C 20 )alkyl, substituted hetero-(C 1 -C 20 )alkyl, hetero-(C 1 -C 20 )alkenyl, substituted hetero-(C 1 -C 20 )alkenyl, hetero-(C 1 -C 20 )alkynyl, substituted hetero-(C 1 -C 20 )alkynyl, (C 1 -C 20 )cycloalkyl, substituted (C 1 -C 20 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle;

R 5 and R 6 are independently selected from the group consisting of H, D, FG, (C 1 -C 20 )alkyl, substituted (C 1 -C 20 )alkyl, (C 1 -C 20 )alkenyl, substituted (C 1 -C 20 )alkenyl, (C 1 -C 20 )alkynyl, substituted (C 1 -C 20 )alkynyl, hetero-(C 1 -C 20 )alkyl, substituted hetero-(C 1 -C 20 )alkyl, hetero-(C 1 -C 20 )alkenyl, substituted hetero-(C 1 -C 20 )alkenyl, hetero-(C 1 -C 20 )alkynyl, substituted hetero-(C 1 -C 20 )alkynyl, (C 1 -C 20 )cycloalkyl, substituted (C 1 -C 20 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle, or are linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;

R 7 and R 8 are independently selected from the group consisting of H, D, FG, (C 1 -C 20 )alkyl, substituted (C 1 -C 20 )alkyl, (C 1 -C 20 )alkenyl, substituted (C 1 -C 20 )alkenyl, (C 1 -C 20 )alkynyl, substituted (C 1 -C 20 )alkynyl, hetero-(C 1 -C 20 )alkyl, substituted hetero-(C 1 -C 20 )alkyl, hetero-(C 1 -C 20 )alkenyl, substituted hetero-(C 1 -C 20 )alkenyl, hetero-(C 1 -C 20 )alkynyl, substituted hetero-(C 1 -C 20 )alkenyl, (C 1 -C 20 )cycloalkyl, substituted (C 1 -C 20 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle, or are linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;

R 9 and R 10 are independently selected from the group consisting of H, D, FG, (C 1 -C 20 )alkyl, substituted (C 1 -C 20 )alkyl, (C 1 -C 20 )alkenyl, substituted (C 1 -C 20 )alkenyl, (C 1 -C 20 )alkynyl, substituted (C 1 -C 20 )alkynyl, hetero-(C 1 -C 20 )alkyl, substituted hetero-(C 1 -C 20 )alkyl, hetero-(C 1 -C 20 )alkenyl, substituted hetero-(C 1 -C 20 )alkenyl, hetero-(C 1 -C 20 )alkynyl, substituted hetero-(C 1 -C 20 )alkenyl, (C 1 -C 20 )cycloalkyl, substituted (C 1 -C 20 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle, or are linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;

R 11 and R 12 are independently selected from the group consisting of H, D, FG, (C 1 -C 20 )alkyl, substituted (C 1 -C 20 )alkyl, (C 1 -C 20 )alkenyl, substituted (C 1 -C 20 )alkenyl, (C 1 -C 20 )alkynyl, substituted (C 1 -C 20 )alkynyl, hetero-(C 1 -C 20 )alkyl, substituted hetero-(C 1 -C 20 )alkyl, hetero-(C 1 -C 20 )alkenyl, substituted hetero-(C 1 -C 20 )alkenyl, hetero-(C 1 -C 20 )alkynyl, substituted hetero-(C 1 -C 20 )alkenyl, (C 1 -C 20 )cycloalkyl, substituted (C 1 -C 20 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle, or are linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;

X 1 -X 8 are independently selected from the group consisting of carbon, oxygen, sulfur, silicon, phosphorous, and nitrogen;

Y 1 -Y 4 are independently selected from H, D, FG, or are absent;

with the proviso that any of R 1 , R 2 , R 3 , or R 4 are absent if bound to an X that is an N.

2. The conductive COF of claim 1 , wherein the one or more cores has a structure of Formula I:

wherein,

R 1 -R 4 are independently selected from the group consisting of H, D, FG, (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, (C 1 -C 6 )cycloalkyl, substituted (C 1 -C 6 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle;

R 5 and R 6 are independently selected from the group consisting of H, D, FG, (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, (C 1 -C 6 )cycloalkyl, substituted (C 1 -C 6 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle, or are linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;

R 7 and R 8 are independently selected from the group consisting of H, D, FG, (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, (C 1 -C 6 )cycloalkyl, substituted (C 1 -C 6 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle, or are linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;

R 9 and R 10 are independently selected from the group consisting of H, D, FG, (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, (C 1 -C 6 )cycloalkyl, substituted (C 1 -C 6 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle, or are linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;

R 11 and R 12 are independently selected from the group consisting of H, D, FG, (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, (C 1 -C 6 )cycloalkyl, substituted (C 1 -C 6 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle, or are linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;

X 1 -X 8 are independently selected from the group consisting of carbon and nitrogen;

Y 1 -Y 4 are independently selected from H, D, FG, or are absent; and

with the proviso that any of R 1 , R 2 , R 3 , or R 4 are absent if bound to an X that is an N.

3. The conductive COF of claim 1 , further comprising a core having a structure of Formula Ia:

wherein,

R 60 -R 79 are independently selected from the group consisting of H, D, FG, (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, (C 1 -C 6 )cycloalkyl, substituted (C 1 -C 6 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle;

R 5 and R 6 are independently selected from the group consisting of H, D, FG, (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, (C 1 -C 6 )cycloalkyl, substituted (C 1 -C 6 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle, or are linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;

R 7 and R 8 are independently selected from the group consisting of H, D, FG, (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, (C 1 -C 6 )cycloalkyl, substituted (C 1 -C 6 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle, or are linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;

R 9 and R 10 are independently selected from the group consisting of H, D, FG, (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, (C 1 -C 6 )cycloalkyl, substituted (C 1 -C 6 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle, or are linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;

R 11 and R 12 are independently selected from the group consisting of H, D, FG, (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, (C 1 -C 6 )cycloalkyl, substituted (C 1 -C 6 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle, or are linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle.

4. The conductive COF of claim 3 , wherein one or more cores has a structure of Formula Ia:

wherein,

R 5 -R 12 , R 60 -R 61 , R 63 -R 66 , R 68 -R 71 , R 73 -R 76 , R 78 -R 79 are H; and

R 62 , R 67 , R 72 , and R 77 are amine or aldehyde groups.

5. The conductive COF of claim 1 , wherein the one or more linking moieties has a structure selected from the group consisting of Formula VII, VIII, and IX:

wherein:

n is a number from 1 to 8;

A 28 -A 44 are independently selected from C or N;

R 96 -R 125 are independently selected from the group consisting of H, D, FG, (C 1 -C 20 )alkyl, substituted (C 1 -C 20 )alkyl, (C 1 -C 20 )alkenyl, substituted (C 1 -C 20 )alkenyl, (C 1 -C 20 )alkynyl, substituted (C 1 -C 20 )alkynyl, hetero-(C 1 -C 20 )alkyl, substituted hetero-(C 1 -C 20 )alkyl, hetero-(C 1 -C 20 )alkenyl, substituted hetero-(C 1 -C 20 )alkenyl, hetero-(C 1 -C 20 )alkynyl, substituted hetero-(C 1 -C 20 )alkynyl, (C 1 -C 20 )cycloalkyl, substituted (C 1 -C 20 )cycloalkyl, aryl, substituted aryl, heterocycle, and substituted heterocycle;

with the proviso that any of R 98 , R 99 , R 101 , R 103 , R 105 -R 108 , R 110 , R 113 , R 115 -R 117 , R 120 , and R 122 -R 124 are absent if bound to an X that is an N.

6. The conductive COF of claim 1 , wherein the one or more linking moieties has a structure of:

7. The conductive COF of claim 1 , wherein the one or more linking moieties has a structure selected from the group consisting of:

8. The conductive organic-framework of claim 1 , wherein the framework is post-synthesis functionalized to comprise a metal or conductive moiety.

9. The conductive organic-framework of claim 1 , wherein the COF has hole conducting mobilities of at least 3.0 cm 2 V −1 s −1 .

10. The conductive organic-framework of claim 9 , wherein the COF has hole conducting mobilities of at least 8.0 cm 2 V −1 s −1 .

11. The conductive organic-framework of claim 1 , wherein the COF can hold a charge for at least 75 μs.

12. A flexible display comprising the conductive organic-framework of claim 1 .

13. A semiconductor comprising the conductive organic-framework of claim 1 .

14. A gas storage device comprising the conductive organic-framework of claim 1 .

15. A chemical sensor comprising the conductive organic-framework of claim 1 .

16. The COF of claim 1 , wherein the COF has the structure and properties of COF-366.

Assignments (2)
CONFIRMATORY LICENSE Recorded Jun 15, 2018
From: UNIVERSITY OF CALIFORNIA LOS ANGELES
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 046364/0600 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 21, 2017
From: YAGHI, OMAR M.; WAN, SHUN; DOONAN, CHRISTIAN J.; WANG, BO; DENG, HEXIANG
To: THE REGENTS OF THE UNIVERSITY OF CALIFORNIA
Reel/Frame 043062/0062 →
Continuity (3)
Continuation 13876126
Provisional Application 61386927 · Sep 27, 2010
Related Publication 20160247593A1 · Aug 25, 2016