Metal complexes for use as dopants and other uses

Patent metadata

Field	Value
Publication number	US-10038150-B2
Application number	US-201615099089-A
Country	US
Kind code	B2
Filing date	Apr 14, 2016
Priority date	Feb 25, 2011
Publication date	Jul 31, 2018
Grant date	Jul 31, 2018

Abstract

The invention relates to electrochemical devices comprising complexes of cobalt comprising at least one ligand with a 5- or six membered, N-containing heteroring. The complex are useful as p- and n-dopants, as over of electrochemical devices, in particular in organic semiconductors. The complexes are further useful as over-discharge prevention and overvoltage protection agents.

First claim

The invention claimed is:

1. A p-dopant comprising a complex of formula (XX)
M(La) n (Xb) m   (XX)

wherein
M is selected from Cu 2+ , Pd 2+ , Au 2+ , Ag 2+ , and V 2+ ;
n is an integer selected from 1, 2, 3 or 4;
m is an integer selected from 0, 1, 2, or 3;
La is a ligand independently selected from mono-, bi-, or tridentate ligands comprising a moiety independently selected from a moiety according to any one of formulae (XX-1)-(XX-5) and (XX-8)-(XX-69)

wherein:

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 of moieties (XX-1)-(XX-5) and (XX-8)-(XX-69) are independently selected from H, halogen, CI—, Br—, I − , —NO 2 , —OH, —NH 2 , —COOH, —CN, —OCN—, isocyanate group, sulfonyl group, from C1-C6 alkyl, C1-C6 heteroalkyl, C4-C20 aryl group, C4-C20 arylalkyl group and C4-C20 heteroaryl group, wherein heteroatom is selected from N, S, or O, said alkyl, heteroalkyl, arylalkyl and heteroaryl groups being optionally perfluorinated, and from a moiety according to any one of formulae (XXA-1) to (XXG-2) below:

wherein:
the dotted line represents the bond connecting the substituent of (XXA-1) to (XXG-2) on the ligand La according to any one of formulae (XX-1)-(XX-5) and (XX-8)-(XX-69); and,
R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 of moieties (XXA-1) to (XXG-2) are independently selected from H, halogen, Cl − , Br − , I − , —NO 2 , —OH, —NH 2 , —COOH, —CN, —OCN − , isocyanate group, sulfonyl group and substituents comprising 1 to 40 carbons and 0 to 20 heteroatoms and/or groups selected from —O—, —C(O)—, —C(O)O—, —S—, —S(O)—, SO 2 —, —S(O) 2 O—, —N═, —P═, —NR 13 —, —PR 13 —, —P(O)(OR 13 )—, —P(O)(OR 13 )O—, —P(O)(NR 13 R 13 )—, —P(O)(NR 13 R 13 )O—, —P(O)(NR 13 R 13 )NR 13 —, —S(O)NR 13 —, and —S(O) 2 NR 13 , with R 13 being independently selected from H, C1-C6 alkyl, C4-C20 aryl group, C4-C20 arylalkyl group and C4-C20 heteroaryl group, said alkyl, arylalkyl and heteroaryl groups being optionally perfluorinated;
R′ and R″ are independently selected from —CH 2 R 1 , —CHR 1 R 2 and —CR 1 R 2 R 3 ,
R 1 , R 2 and R 3 being defined as above; and

Xb is a monodentate co-ligand independently selected from H 2 O, Cl − , Br − , I − , CN − , NCO − , NCS − , NCSe, NH 3 , NR 7 R 8 R 9 , or PR 7 R 8 R 9 , wherein R 7 , R 8 , and R 9 are selected independently from substituted or unsubstituted C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, and C4 to C20 aryl.

2. The p-dopant according to claim 1 , wherein the complex of formula (XX) is under cationic form and provided with an anionic species independently selected from ClO 4 − , PF 6 − , BF 4 − , [B(CN) 4 ] − , CF 3 SO 3 − , [(CF 3 SO 2 ) 2 N] − (TFSI), [B(C 6 H 3 (m-CF 3 ) 2 ) 4 ] − , [B(C 6 F 5 ) 4 ] − , [B(C 6 H 5 ) 4 ] − , [Al(OC(CF 3 ) 3 ) 4 ] − , or [CB 11 H 12 ] − .

3. The p-dopant according to claim 1 , wherein M of the complex of formula (XX) is Cu′.

4. The p-dopant according to claim 1 , wherein n of the complex of formula (XX) is 2, 3 or 4.

5. The p-dopant according to claim 1 , wherein, provided that n of the complex of formula (XX) is 2, said La ligands of the complex of formula (XX) are identical or different from each other.

6. The p-dopant according to claim 1 , wherein m of the complex of formula (XX) is 0.

7. The p-dopant according to claim 1 , wherein La of the complex of formula (XX) is a ligand selected from a moiety according to any one of formulae (XX-1)-(XX-5) and (XX-66) to (XX-69).

8. The p-dopant according to claim 1 , wherein, provided that m is 0, the complex of formula (XX) is selected from a complex according to any one of formulae (XXIII) to (XXV)
M L1 L2 L3 L4  (XXIII),

wherein L1, L2, L3 and L4 are selected from monodentate ligands,
M L1 L2 L3  (XXIV),

wherein L1 and L2 are selected from monodentate ligands and L3 is selected from bidentate ligands,
M L1 L2  (XXV),

wherein L1 and L2 are selected from bidentate ligands, or L1 is selected from monodentate ligands and L2 is selected from tridentate ligands;
wherein said mono-, bi-, or tridentate ligands are independently selected from La ligand.

9. The p-dopant according to claim 1 , wherein the complex of formula (XX) is selected from a complex according to any one of formulae (XXI) and (XXII)

wherein,
R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 and R 29 of complexes (XXI)-(XXII) are independently selected from H, halogen, CI—, Br—, I − , —NO 2 , —OH, —NH 2 , —COOH, —CN, —OCN—, isocyanate group, sulfonyl group, from C1-C6 alkyl, C1-C6 heteroalkyl, C4-C20 aryl group, C4-C20 arylalkyl group and C4-C20 heteroaryl group, wherein heteroatom is selected from N, S, or O, said alkyl, heteroalkyl, arylalkyl and heteroaryl groups being optionally perfluorinated, and from a moiety according to any one of formulae (XXA-I) to (XXG-2) below:

wherein:
the dotted line represents the bond connecting the substituent of (XXA-1) to (XXG-2) on the ligand La according to any one of formulae (XX-1)-(XX-5) and (XX-8)-(XX-69); and,
R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 of moieties (XXA-1) to (XXG-2) are independently selected from H, halogen, Cl − , Br − , 1 − , −NO 2 , —OH, —NH 2 , —COOH, —CN, —OCN −

Assignees

• Ecole Polytechnique Fed Lausanne Epfl

Inventors

• Burschka Julian
• Kessler Florian
• Baranoff Etienne
• Nazeeruddin Mohammad Khaja
• Graetzel Michael
• Zakeeruddin Shaik Mohammed
• Hagfeldt Anders
• Freitag Marina
• Giordano Fabrizio

Classifications

• H01L51/0083 Primary

  Electricity · mapped topic

• Y02E10/549

  Organic PV cells · CPC title

• H01L51/002

  Electricity · mapped topic

• H01L51/4226

  Electricity · mapped topic

• C07F15/065 Primary

  without a metal-carbon linkage · CPC title