Metal complexes for use as dopants and other uses
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.
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 − , 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.
10. An electrochemical and/or optoelectronic device being a solid state solar cell comprising the p-dopant as defined in claim 1 .
11. The electrochemical and/or optoelectronic device according to claim 10 , wherein the p-dopant comprises a complex being 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-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.
12. The electrochemical and/or optoelectronic device according to claim 10 further comprising an organic-inorganic perovskite as light absorber under the form of a layer.
13. The electrochemical and/or optoelectronic device according to claim 10 , 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 ] − , CF3SO 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 ] − .
14. The electrochemical and/or optoelectronic device according to claim 10 , wherein M of the complex of formula (XX) is Cu 2+ .
15. The electrochemical and/or optoelectronic device according to claim 10 , wherein n of the complex of formula (XX) of the p-dopant is 2, 3 or 4.
16. The electrochemical and/or optoelectronic device according to claim 10 , wherein n of the complex of formula (XX) is 2, 3 or 4.
17. The electrochemical and/or optoelectronic device according to claim 10 , wherein m of the complex of formula (XX) is 0.
18. The electrochemical and/or optoelectronic device according to claim 10 , 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).
19. The electrochemical and/or optoelectronic device according to claim 10 , 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.