Supramolecular polymers derived from perylene-diimides

Patent metadata

Field	Value
Publication number	US-9701784-B2
Application number	US-201514636227-A
Country	US
Kind code	B2
Filing date	Mar 3, 2015
Priority date	Mar 26, 2008
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

Abstract

This invention is directed to perylene-diimide aromatic dianion compounds, process of preparation and uses thereof. The perylene-diimide aromatic dianion compounds of this invention are stable in aqueous solution and can be used for photofunctional and electron transfer systems in aqueous phase. This invention is also directed to supramolecular polymers derived from perylene-diimide compounds and mixtures thereof, and to uses thereof.

First claim

What is claimed is:

1. A compound represented by the structure of formula VIa or VIb:

wherein
R 1 is [(CH 2 ) n O] o CH 3 , [(CH 2 ) n C(O)O] o CH 3 , [(CH 2 ) n C(O)NH] o CH 3 , [(CH 2 ) n CH 2 ═CH 2 ] o CH 3 , [(CH 2 ) n CH≡CH] o CH 3 , [(CH 2 ) n NH] o CH 3 , linear or branched (C 1 -C 32 )alkyl, (C 3 -C 8 )cycloalkyl, aryl, heteroaryl, (C 1 -C 32 )alkyl-COOH, (C 1 -C 32 )alkyl-Si-A, or [C(O)CHR 3 NH] p H wherein said aryl or heteroaryl groups are optionally substituted by 1-3 substituents selected from halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and O—(C 1 -C 6 alkyl); wherein A comprises three same or different of the following substituents Cl, Br, I, O(C 1 -C 8 )alkyl or (C 1 -C 8 )alkyl; and wherein R 3 in said [C(O)CHR 3 NH] p H is independently the same or different H, (C 1 -C 6 )alkyl, (C 1 -C 6 )hydroxyalkyl, (C 1 -C 6 )mercaptoalkyl, (C 1 -C 6 )aminoalkyl, (C 1 -C 6 )carboxyalkyl, (C 1 -C 6 )carboxamidoalkyl, (C 1 -C 6 )guanidinoalkyl, aryl, (aryl)alkyl, heteroaryl or (heteroaryl)alkyl;
R 2 is [(CH 2 ) q O] r CH 3 , [(CH 2 ) q C(O)O] r CH 3 , [(CH 2 ) q C(O)NH] r CH 3 , [(CH 2 ) q CH 2 ═CH 2 ] r CH 3 , [(CH 2 ) q CH≡CH] r CH 3 , [(CH 2 ) q NH] r CH 3 , linear or branched (C 1 -C 32 )alkyl, (C 3 -C 8 )cycloalkyl, aryl, heteroaryl, (C 1 -C 32 )alkyl-COOH, (C 1 -C 32 )alkyl-Si-A, or [C(O)CHR 4 NH] s H wherein said aryl or heteroaryl groups are optionally substituted by substituents selected from halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and O—(C 1 -C 6 alkyl); wherein A comprises three same or different of the following substituents Cl, Br, I, O(C 1 -C 8 )alkyl or (C 1 -C 8 )alkyl; and wherein R 4 in said [C(O)CHR 4 NH] s H is independently the same or different H, (C 1 -C 6 )alkyl, (C 1 -C 6 )hydroxyalkyl, (C 1 -C 6 )mercaptoalkyl, (C 1 -C 6 )aminoalkyl, (C 1 -C 6 )carboxyalkyl, (C 1 -C 6 )carboxamidoalkyl, (C 1 -C 6 )guanidinoalkyl, aryl, (aryl)alkyl, heteroaryl or (heteroaryl)alkyl;
R 5 is —OR x where R x is C 1 -C 6 alkyl or [(CH 2 ) n O] o CH 3 , aryl, heteroaryl, C≡C—R 7 , CH═CR 8 R 9 , NR 10 R 11 or a saturated carbocyclic or heterocyclic ring wherein said saturated heterocyclic ring or heteroaryl contains at least one nitrogen atom and R 5 is connected via the nitrogen atom and wherein said saturated carbocyclic ring, heterocyclic ring, aryl and heteroaryl groups are optionally substituted by 1-3 substituents selected from halide, aryl, heteroaryl, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and O—(C 1 -C 6 alkyl);
R 7 is H, halo, (C 1 -C 32 )alkyl, aryl, heteroaryl, Si(H) 3 or Si[(C 1 -C 8 )alkyl] 3 wherein said aryl or heteroaryl groups are optionally substituted by 1-3 substituents selected from halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and O—(C 1 -C 6 alkyl);
R 8 , R 9 , R 10 and R 11 are independently H, (C 1 -C 32 )alkyl, aryl or heteroaryl wherein said aryl or heteroaryl groups are optionally substituted by 1-3 substituents selected from halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and O—(C 1 -C 6 alkyl);
L is an ethynyl group or a diethynylbenzene group;
P is a perylene-diimide group represented by the structure of formula Va or Vb:

n is an integer from 1-5;
o is an integer from 1-100;
p is an integer from 1-100;
q is an integer from 2-5;
r is an integer from 1-100; and
s is an integer from 1-100;
or a metal complex thereof.

2. The compound of claim 1 , wherein R 1 and R 2 are both linear or branched (C 1 -C 32 )alkyl, R 5 is —OR x where R x is (C 1 -C 6 )alkyl or [(CH 2 ) n O] o CH 3 and n is 2 or 3 and o is an integer from 1-100.

3. The compound of claim 1 , wherein o is between 10-20.

4. The compound of claim 1 , wherein o is between 40-50.

5. The compound of claim 1 , wherein o is 44.

6. The compound of claim 1 , wherein o is 13.

7. The compound of claim 1 , wherein o is 23.

8. A supramolecular structure comprising a mixture of at least two different compounds of claim 1 , each has a different size of PEG as represented by a different R 5 for each compound, wherein R 5 is OR x , wherein R x is [(CH 2 ) n O] o CH 3 , n is 2 and “o” is different for each compound.

9. A compound represented by the structure of formula VIa or VIb:

wherein
R 1 is [(CH 2 ) n O] o CH 3 , [(CH 2 ) n C(O)O] o CH 3 , [(CH 2 ) n C(O)NH] o CH 3 , [(CH 2 ) n CH 2 ═CH 2 ] o CH 3 , [(CH 2 ) n CH≡CH] o CH 3 , [(CH 2 ) n NH] o CH 3 , linear or branched (C 1 -C 32 )alkyl, (C 3 -C 8 )cycloalkyl, aryl, heteroaryl, (C 1 -C 32 )alkyl-COOH, (C 1 -C 32 )alkyl-Si-A, or [C(O)CHR 3 NH] p H wherein said aryl or heteroaryl groups are optionally substituted by 1-3 substituents selected from halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and O—(C 1 -C 6 alkyl); wherein A comprises three same or different of the following substituents Cl, Br, I, O(C 1 -C 8 )alkyl or (C 1 -C 8 )alkyl; and wherein R 3 in said [C(O)CHR 3 NH] p H is independently the same or different H, (C 1 -C 6 )alkyl, (C 1 -C 6 )hydroxyalkyl, (C 1 -C 6 )mercaptoalkyl, (C 1 -C 6 )aminoalkyl, (C 1 -C 6 )carboxyalkyl, (C 1 -C 6 )carboxamidoalkyl, (C 1 -C 6 )guanidinoalkyl, aryl, (aryl)alkyl, heteroaryl or (heteroaryl)alkyl;
R 2 is [(CH 2 ) q O] r CH 3 , [(CH 2 ) q C(O)O] r CH 3 , [(CH 2 ) q C(O)NH] r CH 3 , [(CH 2 ) q CH 2 ═CH 2 ] r CH 3 , [(CH 2 ) q CH≡CH] r CH 3 , [(CH 2 ) q NH] r CH 3 , linear or branched (C 1 -C 32 )alkyl, (C 3 -C 8 )cycloalkyl, aryl, heteroaryl, (C 1 -C 32 )alkyl-COOH, (C 1 -C 32 )alkyl-Si-A, or [C(O)CHR 4 NH] s H wherein said aryl or heteroaryl groups are optionally substituted by substituents selected from halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and O—(C 1 -C 6 alkyl); wherein A comprises three same or different of the following substituents Cl, Br, I, O(C 1 -C 8 )alkyl or (C 1 -C 8 )alkyl; and wherein R 4 in said [C(O)CHR 4 NH] s H is independently the same or different H, (C 1 -C 6 )alkyl, (C 1 -C 6 )hydroxyalkyl, (C 1 -C 6 )mercaptoalkyl, (C 1 -C 6 )aminoalkyl, (C 1 -C 6 )carboxyalkyl, (C 1 -C 6 )carboxamidoalkyl, (C 1 -C 6 )guanidinoalkyl, aryl, (aryl)alkyl, heteroaryl or (heteroaryl)alkyl;
R 5 is —OR x where R x is C 1 -C 6 alkyl or [(CH 2 ) n O] o CH 3 , aryl, heteroaryl, C≡C—R 7 , CH═CR 8 R 9 , NR 10 R 11 or a saturated carbocyclic or heterocyclic ring wherein said saturated heterocyclic ring or heteroaryl contains at least one nitrogen atom and R 5 is connected via the nitrogen atom and wherein said saturated carbocyclic ring, heterocyclic ring, aryl and heteroaryl groups are optionally substituted by 1-3 substituents selected from halide, aryl, heteroaryl, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and O—(C 1 -C 6 alkyl);
R 7 is H, halo, (C 1 -C 32 )alkyl, aryl, heteroaryl, Si(H) 3 or Si[(C 1 -C 8 )alkyl] 3 wherein said aryl or heteroaryl groups are optionally substituted by 1-3 substituents selected from halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and O—(C 1 -C 6 alkyl);
R 8 , R 9 , R 10 and R 11 are independently H, (C 1 -C 32 )alkyl, aryl or heteroaryl wherein said aryl or heteroaryl groups are optionally substituted by 1-3 substituents selected from halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and O—(C 1 -C 6 alkyl);
L is a diethynyldipyridine group;
P is a perylene-diimide group represented by the structure of formula Va or Vb:

Assignees

• Yeda Res & Dev

Inventors

• Rybtchinski Boris
• Shirman Elijah
• Ustinov Alona
• Ben-Shitrit Netanel
• Weissman Haim
• Krieg Elisha M
• Golubkov Galina
• Baram Jonathan

Classifications

• C07F15/0093

  without a metal-carbon linkage · CPC title

• C07D471/06

  Peri-condensed systems · CPC title

• C07F15/0066

  without a metal-carbon linkage · CPC title

• C08G2261/374

  of Os, Ir, Pt, Ru, Rh, Pd · CPC title

• H01L51/0067

  Electricity · mapped topic