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 complex of formula (I):
M(La) n (Xb) m (I)
being a dopant,
wherein:
M is a metal selected from Co;
n is an integer from 1 to 6 and a is a consecutive number of a first set consisting of the integers of 1 to n (1, . . . , n), so that there are n ligands L1, . . . , Ln;
m is 0 or an integer from 1 to 5 and b is a consecutive number of a second set consisting of 0 and integers of 1 to m (0, . . . , m), so that if m>0 there are m ligands X1, . . . , Xm;
wherein n and m equal the appropriate number of ligands present on metal M;
wherein any La (L1, . . . , Ln) is independently selected from a mono-, bi-, or tridentate ligand, with the proviso that at least one of said ligands La (L1, . . . , Ln) is, independently, selected from compounds of formulae (1-3) to (3-3) below:
wherein, said ligand comprises at least one substituent R 1 , R 5 , and/or R 8 , as applicable, being selected independently from the substituent (A-1) to (G-2) below:
wherein:
the dotted line represents the bond connecting the substituent of (A-1) to (G-2)) on the compound of formula (1-3), (2-3) or (3-3); and,
substituents R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , in as far as present, are independently selected from H, halogen, —NO 2 , —OH, —NH 2 , and from hydrocarbons comprising 1 to 30 carbons and 0 to 15 heteroatoms;
R′ of substituents (B-10), (C-9), (C-12), (C-14), and (C-16) is selected from C1-C5 alkyl;
wherein at least 3 ligands La are of identical structure (L1=L2=L3); 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 , and PR 7 R 8 R 9 , wherein R 7 , R 8 , and R 9 are selected independently from substituted or unsubstituted alkyl, alkenyl, alkynyl and aryl.
2. The complex according to claim 1 , wherein n is 3 (M L1 L2 L3) and m is 0.
3. The complex according to claim 1 , which is cationic.
4. The complex according to claim 3 , which is provided together with a suitable anionic species selected from the group consisting of halogen (Cl − , Br − , F − ), CN − , NCO − , NCS − , NCSe − , ClO 4 − (perchlorate), PF 6 (hexafluorophosphate), BF 4 (tetrafluoroborate), B(CN) 4 (tetracyanoborate), CF 3 SO 3 (trifluoromethanesulfonate, triflate), (CF 3 SO 2 ) 2 N (Bis(trifluoromethane)sulfonamide, TFSI), B(C 6 H 3 (m-CF 3 ) 2 ) 4 (tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, BARF), B(C 6 F 5 ) 4 (tetrakis(pentafluorophenyl)borate), B(Ph) 4 (tetraphenylborate), Al(OC(CF 3 ) 3 ) 4 , and CB 11 H 12 (carborane anion).
5. A complex of formula (I):
M(La) n (Xb) m (I)
being a dopant,
wherein:
M is a metal selected from Co;
n is an integer from 1 to 6 and a is a consecutive number of a first set consisting of the integers of 1 to n (1, . . . , n), so that there are n ligands L1, . . . , Ln;
m is 0 or an integer from 1 to 5 and b is a consecutive number of a second set consisting of 0 and integers of 1 to m (0, . . . , m), so that if m>0 there are m ligands X1, . . . , Xm;
wherein n and m equal the appropriate number of ligands present on metal M;
wherein any La (L1, . . . , Ln) is independently selected from a mono-, bi-, or tridentate ligand, with the proviso that at least one of said ligands La (L1, . . . , Ln) is, independently, selected from compounds of formulae (1-3) to (3-3) below:
wherein, said ligand comprises at least one substituent R 1 , R 5 , and/or R 8 , as applicable, being selected independently from the substituent (A-1) to (G-2) below:
wherein:
the dotted line represents the bond connecting the substituent of (A-1) to (G-2)) on the compound of formula (1-3), (2-3) or (3-3); and,
substituents R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , in as far as present, are independently selected from H, halogen, —NO 2 , —OH, —NH 2 , and from hydrocarbons comprising 1 to 30 carbons and 0 to 15 heteroatoms;
R′ of substituents (B-10), (C-9), (C-12), (C-14), and (C-16) is selected from C1-C5 alkyl;
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 , and PR 7 R 8 R 9 , wherein R 7 , R 8 , and R 9 are selected independently from substituted or unsubstituted alkyl, alkenyl, alkynyl and aryl; and
wherein said complex of formula (I) is cationic.
6. The complex according to claim 5 , wherein n is 2 (M L1 L2) or 3 (M L1 L2 L3) and m is 0.
7. The complex according to claim 5 , which comprises at least 3 ligands La of identical structure (L1=L2=L3).
8. The complex according to claim 5 , which is provided together with a suitable anionic species selected from the group consisting of halogen (Cl − , Br − , I − ), CN − , NCO − , NCS − , NCSe − , ClO 4 − (perchlorate), PF 6 (hexafluorophosphate), BF 4 (tetrafluoroborate), B(CN) 4 (tetracyanoborate), CF 3 SO 3 (trifluoromethanesulfonate, triflate), (CF 3 SO 2 ) 2 N (Bis(trifluoromethane)sulfonamide, TFSI), B(C 6 H 3 (m-CF 3 ) 2 ) 4 (tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, BARF), B(C 6 F 5 ) 4 (tetrakis(pentafluorophenyl)borate), B(Ph) 4 (tetraphenylborate), Al(OC(CF 3 ) 3 ) 4 , and CB 11 H 12 (carborane anion).
9. A complex of formula (I):
M(La) n (Xb) m (I)
being a dopant,
wherein:
M is a metal selected from Co;
n is an integer from 1 to 6 and a is a consecutive number of a first set consisting of the integers of 1 to n (1, . . . , n), so that there are n ligands L1, . . . , Ln;
m is 0 or an integer from 1 to 5 and b is a consecutive number of a second set consisting of 0 and integers of 1 to m (0, m), so that if m>0 there are m ligands X1, . . . , Xm;
wherein n and m equal the appropriate number of ligands present on metal M;
wherein any La (L1, . . . , Ln) is independently selected from a mono-, bi-, or tridentate ligand, with the proviso that at least one of said ligands La (L1, . . . , Ln) is, independently, selected from compounds of formulae (1-3) to (3-3) below:
wherein, said ligand comprises at least one substituent R 1 , R 5 , and/or R 8 , as applicable, being selected independently from the substituent (A-1) to (G-2) below:
wherein:
the dotted line represents the bond connecting the substituent of (A-1) to (G-2)) on the compound of formula (1-3), (2-3) or (3-3); and,
substituents R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , in as far as present, are independently selected from H, halogen, —NO 2 , —OH, —NH 2 , and from hydrocarbons comprising 1 to 30 carbons and 0 to 15 heteroatoms;
R′ of substituents (B-10), (C-9), (C-12), (C-14), and (C-16) is selected from C1-C5 alkyl;
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 , and PR 7 R 8 R 9 , wherein R 7 , R 8 , and R 9 are selected independently from substituted or unsubstituted alkyl, alkenyl, alkynyl and aryl; and
wherein said complex of formula (I) is cationic and is provided together with a suitable anionic species selected from the group consisting of halogen (Cl − , Br − , I − ), CN − , NCO − , NCS − , NCSe − , ClO 4 − (perchlorate), PF 6 (hexafluorophosphate), BF 4 (tetrafluoroborate), B(CN) 4 (tetracyanoborate), CF 3 SO 3 (trifluoromethanesulfonate, triflate), (CF 3 SO 2 ) 2 N (Bis(trifluoromethane)sulfonamide, TFSI), B(C 6 H 3 (m-CF 3 ) 2 ) 4 (tetrakis[3, 5-bis(trifluoromethyl)phenyl]borate, BARF), B(C 6 F 5 ) 4 (tetrakis(pentafluorophenyl)borate), B(Ph) 4 (tetraphenylborate), Al(OC(CF 3 ) 3 ) 4 , and CB 11 H 12 (carborane anion).
10. The complex according to claim 9 , wherein n is 2 (M L1 L2) or 3 (M L1 L2 L3) and m is 0.
11. The complex according to claim 9 , which comprises at least 3 ligands La of identical structure (L1=L2=L3).