Materials for organic electroluminescent devices
View Patent ↗The present invention relates to metal complexes of the general formulae I to V, in particular as emitter molecules in organic electronic devices, to ligands of the general formulae Ia to Va, and to the use thereof for the preparation of metal complexes, to a layer and an electronic device which comprise the compounds according to the invention, and to a process for the preparation of the compounds according to the invention.
1. A compound of the general formula I
wherein the symbols and indices have the following meanings:
M is Mo, W, Ru, Os, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, or in that the metal M is a main-group metal or main-group metal ion, alkali metals, alkaline-earth metals, Al, Ga or In;
L is, identically or differently on each occurrence, a neutral, cationic or anionic ligand;
X is, identically or differently on each occurrence, C or N;
Z is, identically or differently on each occurrence, N or P;
Cy is, identically or differently on each occurrence, an aryl or heteroaryl group or a cyclic carbene, in each case having 5 to 16 ring atoms, which is selected from the group consisting of phenyl, naphthyl, anthracyl, phenanthryl, biphenyl, pyridyl, 1,3-diazolyl, 1,3-diazocyclopentyl and benzo-1,3-diazolyl, each of which is optionally substituted by one or more radicals R 1 ;
Ar is, identically or differently on each occurrence, a mono- or polycyclic aryl or heteroaryl group having 5 to 60 ring atoms, which is optionally substituted by one or more radicals R 1 , with the proviso that the C atoms which bond to X or Z are constituents of the group Ar;
R 1 is, identically or differently on each occurrence, and are H, D, F, Cl, Br, I, CN, NO 2 ,
a straight-chain C 1-40 -alkyl group, C 1-40 -alkoxy group, thio-C 1-40 -alkyl group, a branched or cyclic C 3-40 -alkyl group, C 3-40 -alkoxy group or thio-C 3-40 -alkoxy group,
each of which is optionally substituted by one or more radicals R 3 ,
where one or more non-adjacent CH 2 groups is optionally replaced by R 5 C═CR 5 , C≡C, Si(R 5 ) 2 , Ge(R 5 ) 2 , Sn(R 5 ) 2 , C═O, C═S, C═Se, C═NR 5 , P(═O)(R 5 ), SO, SO 2 , NR 5 , O, S or CONR 5 , and
where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , a mono- or polycyclic aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms,
which may in each case be substituted by one or more radicals R 4 ,
where, in the case where two adjacent R 1 in each case form an aromatic or heteroaromatic ring system, these two ring systems is optionally linked to one another by a single bond or a divalent unit G,
an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms,
which is optionally substituted by one or more radicals R 4 , and
a combination of these groups,
where one of the R 1 is optionally linked to an L, forming a penta- or hexadentate ligand; or
where one of the R 1 is optionally linked to an L and an opposite R 1 or R 2 , forming a penta- or hexadentate ligand in the form of a cage;
or
two adjacent R 1 together form an oxo group ═O, a group ═NH or a group ═NR 5 , or
two adjacent R 1 , together with the atom or atoms to which they are bonded, form a 5- or 6-membered aliphatic or aromatic ring, which is optionally substituted by one or more radicals R 4 ,
where one or more of the ring CH 2 groups is optionally replaced by O, S or NR 2 ;
R 2 is, identically or differently on each occurrence, and are a non-bonding electron pair, H, D,
a straight-chain C 1-40 -alkyl group, C 1-40 -alkoxy group or thio-C 1-40 -alkyl group or a branched or cyclic C 3-40 -alkyl group, C 3-40 -alkoxy group or thio-C 3-40 -alkoxy group,
each of which is optionally substituted by one or more radicals R 3 ,
where one or more non-adjacent CH 2 groups is optionally replaced by R 5 C═CR 5 , C≡C, Si(R 5 ) 2 , Ge(R 5 ) 2 , Sn(R 5 ) 2 , C═O, C═S, C═Se, C═NR 5 , P(═O)(R 5 ), SO, SO 2 , NR 5 , O, S or CONR 5 , and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO 2 ,
a mono- or polycyclic aromatic or heteroaromatic ring system having 5 to 60 ring atoms,
which may in each case be substituted by one or more radicals R 4 ,
an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 4 , and
a combination of these groups; or
in the case where Z is equal to N, R 2 may furthermore be equal to O, in which case an amine oxide is formed;
R 3 is, identically or differently on each occurrence, a mono- or polycyclic aromatic or heteroaromatic ring system having 5 to 30 ring atoms, in which one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , where, in the case where two adjacent R 3 in
each case form an aromatic or heteroaromatic ring system, these two ring systems is optionally linked to one another by a single bond or a divalent unit G;
R 4 is, identically or differently on each occurrence, and are a straight-chain C 1-20 -alkyl group or a branched or cyclic C 3-20 -alkyl group,
or
two adjacent R 4 , together with the atoms to which they are bonded, form a 5-, 6-, 7- or 8-membered aliphatic ring,
where one or more of the ring CH 2 groups is optionally replaced by O, S or NR 2 ;
R 5 is selected, identically or differently on each occurrence, and are H, D, a straight-chain C 1-20 -alkyl group or a branched or cyclic C 3-20 -alkyl group, in which in each case one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , a mono- or polycyclic aromatic or heteroaromatic ring system having 5 to 30 ring atoms, in which one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , where, in the case where two adjacent R 5 in each case form an aromatic or heteroaromatic ring system, these two ring systems is optionally linked to one another, or
two adjacent R 5 , together with the atoms to which they are bonded, form a 5-, 6-, 7- or 8-membered aliphatic ring,
where one or more of the ring CH 2 groups is optionally replaced by O, S or NH;
G represents a divalent unit which is selected from the group consisting of C(R 5 ) 2 —, C(R 5 ) 2 —C(R 5 ) 2 , C═O, NR 5 , PR 5 , O and S;
n is, identically or differently on each occurrence, 0 or 1;
m denotes the charge of the complex and can be +4, +3, +2, +1, 0, −1, −2, −3 or −4;
A q is a counterion, where q represents the charge of A and can be −4, −3, −2, −1, 0, +1, +2, +3 or +4;
p is 0, 1, 2, 3 or 4;
s is 0 or 1, where, for s=0, a further group R 2 is also bonded to the corresponding Z and a group R 1 is also bonded to the corresponding X.
2. The compound according to claim 1 , wherein the unit Ar is a unit selected from the group consisting of phenyl, naphthyl, anthracyl, phenanthryl and pyridyl, each of which is optionally substituted by one or more radicals R 1 .
3. The compound according to claim 1 , in which the compound of the formula I is a compound of the following formula II:
where the symbols M, L, X, Z, A, R 1 and R 2 and the indices n, m, p, q and s have the same meanings as defined in claim 1 , and the other symbols have the following meanings:
Y is, identically or differently on each occurrence, CR 6 or N; or precisely one Y per ring is NR 6 , S or O if the group W in this ring stands for a bond;
W is, identically or differently on each occurrence, either not present, so that a covalent bond is formed between the two Y bonded to W, or is CR 6 or N, with the proviso that a maximum of two representatives from the unit formed from Y═W—Y can be nitrogen atoms;
R 6 is, identically or differently on each occurrence, and are H, D, F, Cl, Br, I, CN, NO 2 , a C 1-10 -alkyl group, in which one or more 1H atoms is optionally replaced by F, a C 6-18 -aryl group or C 1-18 -heteroaryl group, each of which may carry one or more C 1-6 -alkyl groups as substituents, a 5- to 18-membered heteroaryl group, a C 1-10 -alkoxy group, a C 6-18 -aryloxy group and a 5- to 18-membered heteroaryloxy group, or two R 6 in the vicinal position form a divalent group —CR 7 ═CR 7 —CR 7 ═CR 7 — with one another, or two R 6 in the vicinal position are linked to one another with formation of an aliphatic ring system;
R 7 is, identically or differently on each occurrence, and are H, D, F, Cl, Br, I, CN, NO 2 , a C 1-10 -alkyl group, in which one or more H atoms is optionally replaced by F, a C 6-18 -aryl group, which may carry a C 1-6 -alkyl group as substituent, a 5- to 18-membered heteroaryl group, a C 1-10 -alkoxy group, a C 6-18 -aryloxy group and a 5- to 18-membered heteroaryloxy group, or two R 7 in the vicinal position form a divalent group —CR 8 ═CR 8 —CR═CR 8 — with one another;
R 8 is, identically or differently on each occurrence, and are H, D, F, Cl, Br, I, CN, NO 2 , a C 1-10 -alkyl group, in which one or more H atoms may be replaced by F, a C 6-18 -aryl group, which may carry a C 1-6 -alkyl group as substituent, a 5- to 18-membered heteroaryl group, a C 1-10 -alkoxy group, a C 6-18 -aryloxy group or a 5- to 18-membered heteroaryloxy group.
4. The compound according to claim 1 , in which the compound of the formula I is a compound of the following formula III, IV or V:
where the symbols M, L, X, Y, Z, A, R 1 and R 2 and the indices n, m, p, q and s have the same meanings as defined in claim 1 , and Y stands, identically or differently on each occurrence, for CR 6 ;
where the symbols M, L, Y, Z, A, R 1 and R 2 and the indices n, m, p, q and s have the same meanings as defined claim 1 , and the dashed lines represent either a single covalent bond or a double covalent bond, where, in the case where the dashed line represents a single covalent bond,
U is in each case a CH 2 or C(R 5 ) 2 unit, and, in the case where the dashed line represents a double covalent bond, U is a CR 6 unit, where R 5 and R 6 are as defined in claim 1 ;
where the symbols M, I, Z, X, A, R 1 and R 2 and the indices n, m, p, q and s have the same meanings as defined above, and U is equal to CR 6 , where R 6 is as defined above.
5. The compound according to claim 1 , wherein the symbol X, which coordinates to the metal, is equal to N, Z is equal to N, R 2 is a non-bonding electron pair, and M is equal to Pt, or in that the symbol X, which coordinates to the metal, is equal to C and M is equal to Pt.
6. The compound according to claim 1 , wherein the ligand L is selected, identically or differently on each occurrence, from the group consisting of the following:
CO, NO, SH, OH, carbenes, isonitriles, amines, phosphines, phosphites, arsines, stibines, nitrogen-containing heterocycles, hydride, deuteride, F, Cl, Br, I, alkylacetylides, arylacetylides, heteroarylacetylides, cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, aliphatic or aromatic alcoholates, aliphatic or aromatic thioalcoholates, amides, carboxylates, anionic nitrogen-containing heterocycles and anionic aromatic compounds;
or in that R 1 and L together form a unit which is selected from the group consisting of the following:
—CH 2 CH 2 PMe 2 , —CH 2 CH 2 PPh 2 , —CH 2 CH 2 O − , —CH 2 CH 2 S − , —CH 2 COO − , —CH 2 COS − ,
wherein the position denoted by * is coordinated to the metal M.
7. An oligomer, polymer or dendrimer comprising one or more compounds according to claim 1 , where one or more bonds are present from the compounds of the formula I to the polymer, oligomer or dendrimer.
8. A process for the preparation of the compound according to claim 1 , which comprises reacting a free ligand with a corresponding metal salt to give the complex.
9. A layer comprising at least one compound according to claim 1 .
10. An organic electroluminescent device wherein the compound according to claim 1 is employed as emitting compound in an emitting layer or as charge-transport compound in a charge-transport layer or charge-injection layer.
11. A formulation comprising one or more compounds according to claim 1 and at least one solvent.
12. An electronic device comprising one or more compounds according to claim 1 .
13. The electronic device as claimed in claim 12 , wherein the device is an organic electroluminescent device or polymeric electroluminescent device (OLED, PLED), organic integrated circuit (O-IC), organic field-effect transistor (O-FET), organic thin-film transistor (O-TFT), organic light-emitting transistor (O-LET), organic solar cell (O-SC), organic optical detector, organic photoreceptor, organic field-quench device (O-FQD), light-emitting electrochemical cell (LEC) or organic laser diode (O-laser).
14. The electronic device as claimed in claim 13 , wherein the device is an organic electroluminescent device.
15. A compound of the general formula Ia:
X is, identically or differently on each occurrence, C or N;
Z is, identically or differently on each occurrence, N or P;
Cy is, identically or differently on each occurrence, an aryl or heteroaryl group or a cyclic carbene, in each case having 5 to 16 ring atoms which is selected from the group consisting of phenyl, naphthyl, anthracyl, phenanthryl, biphenyl, pyridyl, 1,3-diazolyl, 1,3-diazocyclopentyl and benzo-1,3-diazolyl, each of which is optionally substituted by one or more radicals R 1 ;
Ar is, identically or differently on each occurrence, a mono- or polycycli aryl or heteroarvl group having 5 to 60 ring atoms, which is optionally substituted by one or more radicals R 1 , with the proviso that the C atoms which bond to X or Z are constituents of the group Ar;
R 1 is, identically or differently on each occurrence, and are H, D, F, Cl, Br, I, CN, NO 2 , a straight-chain C 1-40 -alkyl group, C 1-40 alkoxyy group, thio C 1-40 -alkyl group, a branched or cyclic C 3-40 -alkyl group, C 3-40 -alkoxy group or thio-C 3-40 -alkoxy group, each of which is optionally substituted by one or more radicals R 3 , where one or more non-adjacent CH 2 groups is optionally replaced by R 5 C═CR 5 , C≡C, Si(R 5 ) 2 , Ge(R 5 ) 2 , Sn(R 5 ) 2 , C═O, C═S, C═Se, C═NR 5 , P(═O)(R 5 ), SO, SO 2 , NR 5 , O, S or CONR 5 , and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , a mono- or polycyclic aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 4 , where, in the case where two adjacent R 1 in each case form an aromatic or heteroaromatic ring system, these two ring systems is optionally linked to one another by a single bond or a divalent unit G, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 4 , and a combination of these groups, where one of the R 1 is optionally linked to an I, forming a penta- or hexadentate ligand; or
where one of the R 1 is optionally linked to an L and an opposite R 1 or R 2 , forming a penta- or hexadentate ligand in the form of a cage; or
two adjacent R 1 together form an oxo group ═O, a group ═NH or a group ═NR 5 , or two adjacent R 1 , together with the atom or atoms to which they are bonded, form a 5- or 6-membered aliphatic or aromatic ring, which is optionally substituted by one or more radicals R 4 , where one or more of the ring CH 2 groups is optionally replaced by O, S or NR 2 ;
R 2 is, identically or differently on each occurrence, and are a non-bonding electron pair, H, D,
a straight-chain C 1-40 -alklyl group, C 1-40 -alkoxy group or thio-C 1-40 -alkyl group or a branched or cyclic C 1-40 -alkyl group, C 3-40 -alkoxy group or thio-C 3-40 -alkoxy group,
each of which is optionally substituted by one or more radicals R 3 ,
where one or more non-adjacent CH 2 groups is optionally replaced by R 5 C═CR 5 , C≡C, Si(R 5 ) 2 , Ge(R 5 ) 2 , Sn(R 5 ) 2 , C═O, C═S, C═Se, C═NR 5 , P(═O)(R 5 ), SO, SO 2 , NR 5 , O, S or CONR 5 , and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , a mono- or polycyclic aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case be substituted by one or more radicals R 4 ,
an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms,
which is optionally substituted by one or more radicals R 4 , and
a combination of these groups; or
in the case where Z is equal to N, R 2 may furthermore be equal to O, in which case an amine oxide is formed;
R 3 is, identically or differently on each occurrence, a mono- or polycyclic aromatic or heteroaromatic ring system having 5 to 30 ring atoms, in which one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , where, in the case where two adjacent R 3 in each case form an aromatic or heteroaromatic ring system, these two ring systems is optionally linked to one another by a single bond or a divalent unit G;
R 4 is, identically or differently on each occurrence, and are a straight-chain C 1-20 -alkyl group or a branched or cyclic C 3-20 -alkyl group
or
two adjacent R 4 , together with the atoms to which they are bonded, form a 5-, 6-, 7- or 8-membered aliphatic ring,
where one or more of the ring CH 2 groups is optionally replaced by O, S or NR 2 ;
R 5 is selected, identically or differently on each occurrence, and are H, D, a straight-chain C 1-20 -alkyl group or a branched or cyclic C 3-20 -alkyl group, in which in each case one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , a mono- or polycyclic aromatic or heteroaromatic ring system having 5 to 30 ring atoms, in which one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , where, in the case where two adjacent R 5 in each case form an aromatic or heteroaromatic ring system, these two ring systems is optionally linked to one another, or
two adjacent R 5 , together with the atoms to which they are bonded, form a 5-, 6-, 7- or 8-membered aliphatic ring, where one or more of the ring CH groups is optionally replaced by O, S or NH;
G represents a divalent unit which is selected from the group consisting of C(R 5 ) 2 —, —C(R 5 ) 2 —C(R 5 ) 2 , C═O, NR 5 , PR 5 , O and S; and
E stands, identically or differently on each occurrence, for CH or N.