Methods of preparing multilayered electrochromic systems

Patent metadata

Field	Value
Publication number	US-11053434-B2
Application number	US-201615758344-A
Country	US
Kind code	B2
Filing date	Sep 8, 2016
Priority date	Sep 8, 2015
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

The invention is directed to methods for making an EC material comprising providing a substrate, applying at least one metal linker to the substrate, applying at least one metal-coordinated organic complex to form a layer, washing the layer, drying the layer, and repeating the applying steps to obtain a multiple layer EC material. The invention is further directed to EC materials made by the methods of this invention.

First claim

What is claimed is:

1. A method for making an electrochromic EC material comprising providing a substrate, applying at least one metal linker directly to the substrate, applying at least one metal-coordinated organic complex to form a layer, and repeating the applying steps to obtain a multiple layer EC material, wherein said substrate is not modified with a coupling layer.

2. The method of claim 1 , wherein said metal-coordinated organic complex comprises at least one functional group, said functional group capable of binding to said metal linker.

3. The method of claim 2 , wherein said binding comprises a coordination bond between said functional group and said metal linker.

4. The method of claim 1 , wherein said metal-coordinated organic complex is polypyridyl complex.

5. The method of claim 4 wherein said polypyridyl complex comprises one isomer, or more isomers of the same compound, or a mixture of said isomers.

6. The method of claim 5 , wherein said isomers are enantiomers and wherein said polypyridyl complex comprises one or two enantiomers of the same compound or a mixture of said one or two enantiomers.

7. The method according to claim 4 , wherein the polypyridyl complex is represented by Formula I:

wherein
M is a transition metal selected from Mn, Fe, Co, Ni, Cu, Zn, Ti, C, Cr, Rh, or Ir;
n is the formal oxidation state of the transition metal, wherein n is 0-6;
X is a counter ion;
m is a number ranging from 0 to 6;
R 1 to R 18 each independently is selected from H, halogen, —OH, —N 3 , —NO 2 , —CN, —N(R 20 ) 2 , —CON(R 20 ) 2 , —COOR 20 , —SR 20 , —SO 3 H, —CH═CH-pyridyl, —(C 1 -C 10 )alkyl, —(C 2 -C 10 )alkenyl, —(C 2 -C 10 )alkynyl, —(C 1 -C 10 )alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (C 1 -C 10 )alkyl, (C 2 -C 10 )alkenyl, (C 2 -C 10 )alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, —OR 20 , —COR 20 , —COOR 20 , —OCOOR 20 , —OCON(R 20 ) 2 , —(C 1 -C 8 )alkylene-COOR 20 , —CN, —N(R 20 ) 2 , —NO 2 , —SR 20 , —(C 1 -C 8 )alkyl, —O—(C 1 -C 8 )alkyl, —CON(R 20 ) 2 , or —SO 3 H;
A 1 to A 6 each independently is a group of Formula III, or of Formula IV, linked to the ring structure of the complex of general Formula I via R 19

R 19 each independently is selected from a covalent bond, H 2 C—CH 2 , HC═CH, C≡C, N═N, HC═N, N═CH, H 2 C—NH, HN—CH 2 , —COO—, —CONH—, —CON(OH)—, —NR 20 —, —Si(R 20 ) 2 —, an alkylene optionally interrupted by one or more heteroatoms selected from O, S, or N, phenylene, biphenylene, a peptide moiety consisting of 3 to 5 amino acid residues,

R x and R y each independently is selected from H, halogen, —OH, —N 3 , —NO 2 , —CN, —N(R 20 ) 2 , —CON(R 20 ) 2 , —COOR 20 , —SR 20 , —SO 3 H, —CH═CH-pyridyl, —(C 1 -C 10 )alkyl, —(C 2 -C 10 )alkenyl, —(C 2 -C 10 )alkynyl, —(C 1 -C 10 )alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, protected carboxyl, or protected amino, wherein the (C 1 -C 10 )alkyl, (C 2 -C 10 )alkenyl, (C 2 -C 10 )alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, —OR 20 , —COR 20 , —COOR 20 , —OCOOR 20 , —OCON(R 20 ) 2 , —(C 1 -C 8 )alkylene-COOR 20 , —CN, —N(R 20 ) 2 , —NO 2 , —SR 20 , —(C 1 -C 8 )alkyl, —O—(C 1 -C 8 )alkyl, —CON(R 20 ) 2 , or SO 3 H; and
R 20 each independently is H, (C 1 -C 6 )alkyl, or aryl.

8. The method according to claim 4 , wherein the polypyridyl complex is represented by Formula II:

wherein
n is the formal oxidation state of Fe, wherein n is 0-6;
X is a counter ion;
m is a number ranging from 0 to 6;
R 1 to R 18 each independently is selected from H, halogen, —OH, —N 3 , —NO 2 , —CN, —N(R 20 ) 2 , —CON(R 20 ) 2 , —COOR 20 , —SR 20 , —SO 3 H, —CH═CH-pyridyl, —(C 1 -C 10 )alkyl, —(C 2 -C 10 )alkenyl, —(C 2 -C 10 )alkynyl, —(C 1 -C 10 )alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (C 1 -C 10 )alkyl, (C 2 -C 10 )alkenyl, (C 2 -C 10 )alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, —OR 20 , —COR 20 , —COOR 20 , —OCOOR 20 , —OCON(R 20 ) 2 , —(C 1 -C 8 )alkylene-COOR 20 , —CN, —N(R 20 ) 2 , —NO 2 , —SR 20 , —(C 1 -C 8 )alkyl, —O—(C 1 -C 8 )alkyl, —CON(R 20 ) 2 , or SO 3 H;
A 1 , A 3 , and A 5 each independently is a group of Formula III, or of Formula IV, linked to the ring structure of the complex of general Formula II via R 19

R 19 each independently is selected from a covalent bond, H 2 C—CH 2 , cis/tran HC═CH, C≡C, N═N, HC═N, N═CH, H 2 C—NH, HN—CH 2 , —COO—, —CONH—, —CON(OH)—, —NR 20 —, —Si(R 20 ) 2 —, an alkylene optionally interrupted by one or more heteroatoms selected from O, S, or N, phenylene, biphenylene, a peptide moiety consisting of 3 to 5 amino acid residues,

R x and R y each independently is selected from H, halogen, —OH, —N 3 , —NO 2 , —CN, —N(R 20 ) 2 , —CON(R 20 ) 2 , —COOR 20 , —SR 20 , —SO 3 H, —CH═CH-pyridyl, —(C 1 -C 10 )alkyl, —(C 2 -C 10 )alkenyl, —(C 2 -C 10 )alkynyl, —(C 1 -C 10 )alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, protected carboxyl, or protected amino, wherein the (C 1 -C 10 )alkyl, (C 2 -C 10 )alkenyl, (C 2 -C 10 )alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, —OR 20 , —COR 20 , —COOR 20 , —OCOOR 20 , —OCON(R 20 ) 2 , —(C 1 -C 5 )alkylene-COOR 20 , —CN, —N(R 20 ) 2 , —NO 2 , —SR 20 , —(C 1 -C 5 )alkyl, —O—(C 1 -C 5 )alkyl, —CON(R 20 ) 2 , or —SO 3 H;
B 1 to B 3 each independently is selected from H, halogen, —OH, —N 3 , —NO 2 , —CN, —N(R 20 ) 2 , —CON(R 20 ) 2 , —COOR 20 , —SR 20 , —SO 3 H, —CH═CH-pyridyl, —(C 1 -C 10 )alkyl, —(C 2 -C 10 )alkenyl, —(C 2 -C 10 )alkynyl, —(C 1 -C 10 )alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, protected carboxyl, or protected amino, wherein the (C 1 -C 10 )alkyl, (C 2 -C 10 )alkenyl, (C 2 -C 10 )alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, —OR 20 , —COR 20 , —COOR 20 , —OCOOR 20 , —OCON(R 20 ) 2 , —(C 1 -C 8 )alkylene-COOR 20 , —CN, —N(R 20 ) 2 , —NO 2 , —SR 20 , —(C 1 -C 8 )alkyl, —O—(C 1 -C 8 )alkyl, —CON(R 20 ) 2 , or —SO 3 H; and
R 20 each independently is H, (C 1 -C 6 )alkyl, or aryl.

9. The method according to claim 4 , wherein the polypyridyl complex is represented by one of the following formulas, or by a mixture of the following formulas, or by a combination of the following formulas with molecules with different metal centers or ligands:

10. The method according to claim 4 , wherein the polypyridyl complex is a mixture of polypyridyl complexes.

11. The method of claim 1 , wherein said applying steps comprise roll-to-roll, spin coating, di

Assignees

• Yeda Res & Dev

Inventors

• Van Der Boom Milko E
• Lahav Michal
• Elool Dov Neta

Classifications

• C09D5/29

  for multicolour effects · CPC title

• B05D5/06

  to obtain multicolour or other optical effects (B05D5/02 takes precedence) · CPC title

• G02F1/1516

  comprising organic material · CPC title

• B05D1/005

  Spin coating · CPC title

• C09K9/02 Primary

  Organic tenebrescent materials · CPC title