U.S. patent application number 12/781981 was filed with the patent office on 2010-09-09 for metal complexes.
This patent application is currently assigned to Merck Patent GmbH. Invention is credited to Hubert Spreitzer, Philipp Stoessel.
Application Number | 20100227978 12/781981 |
Document ID | / |
Family ID | 32920758 |
Filed Date | 2010-09-09 |
United States Patent
Application |
20100227978 |
Kind Code |
A1 |
Stoessel; Philipp ; et
al. |
September 9, 2010 |
METAL COMPLEXES
Abstract
The present invention relates to new types of metal complexes.
Such compounds can be used as active components (=functional
materials) in a series of different types of applications which can
be classed within the electronics industry in the widest sense. The
inventive compounds are described by the structure 1 and the
formulae (1) to (60).
Inventors: |
Stoessel; Philipp;
(Frankfurt Am Main, DE) ; Spreitzer; Hubert;
(Viernheim, DE) |
Correspondence
Address: |
Connolly Bove Lodge & Hutz LLP
P. O. Box 2207, 1007 North Orange Street
Wilmington
DE
19899-2207
US
|
Assignee: |
Merck Patent GmbH
Darmstadt
DE
|
Family ID: |
32920758 |
Appl. No.: |
12/781981 |
Filed: |
May 18, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10548855 |
Sep 9, 2005 |
7728137 |
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PCT/EP04/02393 |
Mar 9, 2004 |
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12781981 |
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Current U.S.
Class: |
525/326.7 ;
525/416; 525/417; 546/14; 546/165; 546/21; 546/339; 546/4;
546/6 |
Current CPC
Class: |
C07D 217/16 20130101;
C09B 57/10 20130101; C07F 15/0033 20130101; C07D 213/30
20130101 |
Class at
Publication: |
525/326.7 ;
546/6; 546/21; 546/165; 546/339; 546/14; 546/4; 525/417;
525/416 |
International
Class: |
C07F 5/06 20060101
C07F005/06; C07F 15/00 20060101 C07F015/00; C07F 9/28 20060101
C07F009/28; C07F 7/10 20060101 C07F007/10; C08G 75/00 20060101
C08G075/00; C08G 61/02 20060101 C08G061/02; C08G 73/00 20060101
C08G073/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 11, 2003 |
DE |
103 10 887.4 |
Claims
1.-30. (canceled)
31. A compound of the following formula [V-L.sub.3]M wherein M is a
metal selected from the group consisting of Al, Ga, In, Tl, P, As,
Sb, Bi, Sc, Y, La, V, Nb, Ta, Cr, Mo, W, Fe, Ru, Os, Co, Rh, Ir,
Cu, Au, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; V is a
bridging unit, which contains from 1 to 80 atoms and which connects
the three partial ligands L; L is the same or different on each
occurrence and is a bidentate ligand comprising two cyclic groups
Cy1 and Cy2, which are the same or different on each occurrence
substituted or unsubstituted, saturated, unsaturated or aromatic
homo- or heterocycles, which are each bonded ionically, covalently
or coordinatively to the metal via a ring atom or via an atom
bonded exocyclically to the homo- or heterocycle.
32. A compound according to claim 31 which comprises the structure
1, ##STR00063## containing at least one metal Met, which has the
same meaning as M in claim 31, coordinated to a polypodal ligand
Lig of the structure 2, ##STR00064## where V is a bridging unit,
wherein V contains from 1 to 80 atoms and the three part-ligands
L1, L2 and L3 which may be the same or different at each instance
are covalently bonded to one another, and where the three
part-ligands L1, L2 and L3 satisfy the structure 3 ##STR00065##
wherein Cy1 and Cy2 are the same or different at each instance and
correspond to substituted or unsubstituted, saturated, unsaturated
or aromatic homo- or heterocycles or part-homo- or
part-heterocycles of a fused system, which are each bonded
ionically, covalently or coordinatively to the metal via a ring
atom or via an atom bonded exocyclically to the homo- or
heterocycle, and that the compounds of the structure 1 are
uncharged.
33. The compound as claimed in claim 31, wherein L1=L2=L3.
34. The compound as claimed in claim 31, wherein L1.noteq.L2.
35. The compound as claimed in claim 31, wherein the linking unit V
contains, as the linking atom, an element of main group 3, 4 or 5,
or a 3- to 6-membered homo- or heterocycle.
36. The compound as claimed in claim 31, wherein the polypodal
ligand Lig of the structure 4 generates facial coordination
geometry on the metal Met ##STR00066##
37. The compound as claimed in claim 31, wherein the polypodal
ligand Lig of the structure 5 generates meridional coordination
geometry on the metal Met ##STR00067##
38. The compound as claimed in claim 31, wherein the compound is
selected from the compounds (1) to (8) ##STR00068## ##STR00069##
where the symbols and indices are each defined as follows: M is Al,
Ga, In, Tl, P, As, Sb, Bi, Sc, Y, La, V, Nb, Ta, Cr, Mo, W, Fe, Ru,
Os, Co, Rh, Ir, Cu, Au, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb
or Lu; L is the same or different at each instance and is C, N or
P; Q is the same or different at each instance and is O, S, Se, Te
or N; T is the same or different at each instance and is N, P or C;
X is the same or different at each instance and is CR, N or P; Y is
the same or different at each instance and is NR.sup.1, O, S, Se,
Te, SO, SeO, TeO, SO.sub.2, SeO.sub.2 or TeO.sub.2; Z is B, BR,
B(CR.sub.2).sub.3, B(CR.sub.2CR.sub.2).sub.3, CR, COH, COR.sup.1,
CF, CCl, CBr, C--I, CNR.sup.1.sub.2, RC(CR.sub.2).sub.3,
RC(CR.sub.2CR.sub.2).sub.3, RC(SiR.sub.2).sub.3,
RC(SiR.sub.2CR.sub.2).sub.3, RC(CR.sub.2SiR.sub.2).sub.3,
RC(SiR.sub.2SiR.sub.2).sub.3, cis,cis-1,3,5-cyclohexyl,
1,3,5-(CR.sub.2).sub.3C.sub.6H.sub.3, SiR, SiOH, SiOR.sup.1,
RSi(CR.sub.2).sub.3, RSi(CR.sub.2CR.sub.2).sub.3,
RSi(SiR.sub.2).sub.3, RSi(SiR.sub.2CR.sub.2).sub.3,
RSi(CR.sub.2SiR.sub.2).sub.3, RSi(SiR.sub.2SiR.sub.2).sub.3, N,
N(CR.sub.2).sub.3, N(C.dbd.O).sub.3, N(CR.sub.2CR.sub.2).sub.3, NO,
P, As, Sb, Bi, PO, AsO, SbO, BiO, PSe, AsSE, SbSe, BiSe, PTe, AsTe,
SbTe or BiTe; R is the same or different at each instance and is H,
F, Cl, Br, I, NO.sub.2, CN, a straight-chain or branched or cyclic
alkyl or alkoxy group having from 1 to 20 carbon atoms, in which
one or more nonadjacent CH.sub.2 groups is optionally replaced by
--R.sup.1C.dbd.CR.sup.1--, --C.ident.C--, Si(R.sup.1).sub.2,
Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.1, --O--, --S--, --NR.sup.1-- or --CONR.sup.1--, and
in which one or more hydrogen atoms is optionally replaced by F, or
an aryl or heteroaryl group which has from 1 to 14 carbon atoms and
is optionally substituted by one or more nonaromatic R radicals,
where a plurality of substituents R, both on the same ring and on
the two different rings, together optionally forms a further mono-
or polycyclic, aliphatic or aromatic ring system; R.sup.1 is the
same or different at each instance and is an aliphatic or aromatic
hydrocarbon radical having from 1 to 20 carbon atoms; c is the same
or different at each instance and is 0 or 1.
39. The compound as claimed in claim 31, wherein the compound is
selected from the compounds (9) to (12) ##STR00070## wherein M is
Al, Ga, In, Tl, P, As, Sb, Bi, Sc, Y, La, V, Nb, Ta, Cr, Mo, W, Fe,
Ru, Os, Co, Rh, Ir, Cu, Au, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
Yb or Lu; L is the same or different at each instance and is C, N
or P; Q is the same or different at each instance and is O, S, Se,
Te or N; T is the same or different at each instance and is N, P or
C; X is the same or different at each instance and is CR, N or P; Y
is the same or different at each instance and is NR.sup.1, O, S,
Se, Te, SO, SeO, TeO, SO.sub.2, SeO.sub.2 or TeO.sub.2; Z is B, BR,
B(CR.sub.2).sub.3, B(CR.sub.2CR.sub.2).sub.3, CR, COH, COR.sup.1,
CF, CCl, CBr, C--I, CNR.sup.1.sub.2, RC(CR.sub.2).sub.3,
RC(CR.sub.2CR.sub.2).sub.3, RC(SiR.sub.2).sub.3,
RC(SiR.sub.2CR.sub.2).sub.3, RC(CR.sub.2SiR.sub.2).sub.3,
RC(SiR.sub.2SiR.sub.2).sub.3, cis,cis-1,3,5-cyclohexyl,
1,3,5-(CR.sub.2).sub.3C.sub.6H.sub.3, SiR, SiOH, SiOR.sup.1,
RSi(CR.sub.2).sub.3, RSi(CR.sub.2CR.sub.2).sub.3,
RSi(SiR.sub.2).sub.3, RSi(SiR.sub.2CR.sub.2).sub.3,
RSi(CR.sub.2SiR.sub.2).sub.3, RSi(SiR.sub.2SiR.sub.2).sub.3, N,
N(CR.sub.2).sub.3, N(C.dbd.O).sub.3, N(CR.sub.2CR.sub.2).sub.3, NO,
P, As, Sb, Bi, PO, AsO, SbO, BiO, PSe, AsSE, SbSe, BiSe, PTe, AsTe,
SbTe or BiTe; R is the same or different at each instance and is H,
F, Cl, Br, I, NO.sub.2, CN, a straight-chain or branched or cyclic
alkyl or alkoxy group having from 1 to 20 carbon atoms, in which
one or more nonadjacent CH.sub.2 groups is optionally replaced by
--R.sup.1C.dbd.CR.sup.1--, --C.ident.C--, Si(R.sup.1).sub.2,
Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.1, --O--, --S--, --NR.sup.1-- or --CONR.sup.1--, and
in which one or more hydrogen atoms is optionally replaced by F, or
an aryl or heteroaryl group which has from 1 to 14 carbon atoms and
is optionally substituted by one or more nonaromatic R radicals,
where a plurality of substituents R, both on the same ring and on
the two different rings, together optionally forms a further mono-
or polycyclic, aliphatic or aromatic ring system; R.sup.1 is the
same or different at each instance and is an aliphatic or aromatic
hydrocarbon radical having from 1 to 20 carbon atoms; c is the same
or different at each instance and is 0 or 1 and n is 1 or 2.
40. The compound as claimed in claim 31, wherein the compound is
selected from the compounds (13) to (30) ##STR00071## ##STR00072##
##STR00073## ##STR00074## wherein M is Al, Ga, In, Tl, P, As, Sb,
Bi, Sc, Y, La, V, Nb, Ta, Cr, Mo, W, Fe, Ru, Os, Co, Rh, Ir, Cu,
Au, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu; L is the same
or different at each instance and is C, N or P; Q is the same or
different at each instance and is O, S, Se, Te or N; T is the same
or different at each instance and is N, P or C; X is the same or
different at each instance and is CR, N or P; Y is the same or
different at each instance and is NR.sup.1, O, S, Se, Te, SO, SeO,
TeO, SO.sub.2, SeO.sub.2 or TeO.sub.2; Z is B, BR,
B(CR.sub.2).sub.3, B(CR.sub.2CR.sub.2).sub.3, CR, COH, COR.sup.1,
CF, CCl, CBr, C--I, CNR.sup.1.sub.2, RC(CR.sub.2).sub.3,
RC(CR.sub.2CR.sub.2).sub.3, RC(SiR.sub.2).sub.3,
RC(SiR.sub.2CR.sub.2).sub.3, RC(CR.sub.2SiR.sub.2).sub.3,
RC(SiR.sub.2SiR.sub.2).sub.3, cis,cis-1,3,5-cyclohexyl,
1,3,5-(CR.sub.2).sub.3C.sub.6H.sub.3, SiR, SiOH, SiOR.sup.1,
RSi(CR.sub.2).sub.3, RSi(CR.sub.2CR.sub.2).sub.3,
RSi(SiR.sub.2).sub.3, RSi(SiR.sub.2CR.sub.2).sub.3,
RSi(CR.sub.2SiR.sub.2).sub.3, RSi(SiR.sub.2SiR.sub.2).sub.3, N,
N(CR.sub.2).sub.3, N(C.dbd.O).sub.3, N(CR.sub.2CR.sub.2).sub.3, NO,
P, As, Sb, Bi, PO, AsO, SbO, BiO, PSe, AsSE, SbSe, BiSe, PTe, AsTe,
SbTe or BiTe; R is the same or different at each instance and is H,
F, Cl, Br, I, NO.sub.2, CN, a straight-chain or branched or cyclic
alkyl or alkoxy group having from 1 to 20 carbon atoms, in which
one or more nonadjacent CH.sub.2 groups is optionally replaced by
--R.sup.1C.dbd.CR.sup.1--, --C.ident.C--, Si(R.sup.1).sub.2,
Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.1, --O--, --S--, --NR.sup.1-- or --CONR.sup.1--, and
in which one or more hydrogen atoms is optionally replaced by F, or
an aryl or heteroaryl group which has from 1 to 14 carbon atoms and
is optionally substituted by one or more nonaromatic R radicals,
where a plurality of substituents R, both on the same ring and on
the two different rings, together optionally forms a further mono-
or polycyclic, aliphatic or aromatic ring system; R.sup.1 is the
same or different at each instance and is an aliphatic or aromatic
hydrocarbon radical having from 1 to 20 carbon atoms; c is the same
or different at each instance and is 0 or 1 and n is 1 or 2.
41. The compound as claimed in claim 31, selected from the
compounds (31) to (41) ##STR00075## ##STR00076## ##STR00077##
wherein M is Al, Ga, In, Tl, P, As, Sb, Bi, Sc, Y, La, V, Nb, Ta,
Cr, Mo, W, Fe, Ru, Os, Co, Rh, Ir, Cu, Au, Pr, Nd, Sm, Eu, Gd, Tb,
Dy, Ho, Er, Tm, Yb or Lu; L is the same or different at each
instance and is C, N or P; Q is the same or different at each
instance and is O, S, Se, Te or N; T is the same or different at
each instance and is N, P or C; X is the same or different at each
instance and is CR, N or P; Y is the same or different at each
instance and is NR.sup.1, O, S, Se, Te, SO, SeO, TeO, SO.sub.2,
SeO.sub.2 or TeO.sub.2; Z is B, BR, B(CR.sub.2).sub.3,
B(CR.sub.2CR.sub.2).sub.3, CR, COH, COR.sup.1, CF, CCl, CBr, C--I,
CNR.sup.1.sub.2, RC(CR.sub.2).sub.3, RC(CR.sub.2CR.sub.2).sub.3,
RC(SiR.sub.2).sub.3, RC(SiR.sub.2CR.sub.2).sub.3,
RC(CR.sub.2SiR.sub.2).sub.3, RC(SiR.sub.2SiR.sub.2).sub.3,
cis,cis-1,3,5-cyclohexyl, 1,3,5-(CR.sub.2).sub.3C.sub.6H.sub.3,
SiR, SiOH, SiOR.sup.1, RSi(CR.sub.2).sub.3,
RSi(CR.sub.2CR.sub.2).sub.3, RSi(SiR.sub.2).sub.3,
RSi(SiR.sub.2CR.sub.2).sub.3, RSi(CR.sub.2SiR.sub.2).sub.3,
RSi(SiR.sub.2SiR.sub.2).sub.3, N, N(CR.sub.2).sub.3,
N(C.dbd.O).sub.3, N(CR.sub.2CR.sub.2).sub.3, NO, P, As, Sb, Bi, PO,
AsO, SbO, BiO, PSe, AsSE, SbSe, BiSe, PTe, AsTe, SbTe or BiTe; R is
the same or different at each instance and is H, F, Cl, Br, I,
NO.sub.2, CN, a straight-chain or branched or cyclic alkyl or
alkoxy group having from 1 to 20 carbon atoms, in which one or more
nonadjacent CH.sub.2 groups is optionally replaced by
--R.sup.1C.dbd.CR.sup.1--, --C.ident.C--, Si(R.sup.1).sub.2,
Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.1, --O--, --S--, --NR.sup.1-- or --CONR.sup.1--, and
in which one or more hydrogen atoms is optionally replaced by F, or
an aryl or heteroaryl group which has from 1 to 14 carbon atoms and
is optionally substituted by one or more nonaromatic R radicals,
where a plurality of substituents R, both on the same ring and on
the two different rings, together optionally forms a further mono-
or polycyclic, aliphatic or aromatic ring system; R.sup.1 is the
same or different at each instance and is an aliphatic or aromatic
hydrocarbon radical having from 1 to 20 carbon atoms; c is the same
or different at each instance and is 0 or 1 and n is 1 or 2.
42. A compound which is selected from the compounds of compounds
(42) to (82) ##STR00078## wherein T is the same or different at
each instance and is N, P or C; Y is the same or different at each
instance and is NR.sup.1, O, S, Se, Te, SO, SeO, TeO, SO.sub.2,
SeO.sub.2 or TeO.sub.2; Z is B, BR, B(CR.sub.2).sub.3,
B(CR.sub.2CR.sub.2).sub.3, CR, COH, COR.sup.1, CF, CCl, CBr, C--I,
CNR.sup.1.sub.2, RC(CR.sub.2).sub.3, RC(CR.sub.2CR.sub.2).sub.3,
RC(SiR.sub.2).sub.3, RC(SiR.sub.2CR.sub.2).sub.3,
RC(CR.sub.2SiR.sub.2).sub.3, RC(SiR.sub.2SiR.sub.2).sub.3,
cis,cis-1,3,5-cyclohexyl, 1,3,5-(CR.sub.2).sub.3C.sub.6H.sub.3,
SiR, SiOH, SiOR.sup.1, RSi(CR.sub.2).sub.3,
RSi(CR.sub.2CR.sub.2).sub.3, RSi(SiR.sub.2).sub.3,
RSi(SiR.sub.2CR.sub.2).sub.3, RSi(CR.sub.2SiR.sub.2).sub.3,
RSi(SiR.sub.2SiR.sub.2).sub.3, N, N(CR.sub.2).sub.3,
N(C.dbd.O).sub.3, N(CR.sub.2CR.sub.2).sub.3, NO, P, As, Sb, Bi, PO,
AsO, SbO, BiO, PSe, AsSE, SbSe, BiSe, PTe, AsTe, SbTe or BiTe; R is
the same or different at each instance and is H, F, Cl, Br, I,
NO.sub.2, CN, a straight-chain or branched or cyclic alkyl or
alkoxy group having from 1 to 20 carbon atoms, in which one or more
nonadjacent CH.sub.2 groups is optionally replaced by
--R.sup.1C.dbd.CR.sup.1--, --C.ident.C--, Si(R.sup.1).sub.2,
Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.1, --O--, --S--, --NR.sup.1-- or --CONR.sup.1--, and
in which one or more hydrogen atoms is optionally replaced by F, or
an aryl or heteroaryl group which has from 1 to 14 carbon atoms and
is optionally substituted by one or more nonaromatic R radicals,
where a plurality of substituents R, both on the same ring and on
the two different rings, together optionally forms a further mono-
or polycyclic, aliphatic or aromatic ring system; R.sup.1 is the
same or different at each instance and is an aliphatic or aromatic
hydrocarbon radical having from 1 to 20 carbon atoms; c is the same
or different at each instance and is 0 or 1 X is the same or
different at each instance and is CR or P; ##STR00079## wherein the
symbols and indices T, X, Y, Z, R, R.sup.1, and c are defined
above, ##STR00080## wherein Q is the same or different at each
instance and is O, S, Se, Te or N; wherein the symbols and indices
T, X, Y, Z, R, R.sup.1, and c are defined above, L is the same or
different at each instance and is C or P; ##STR00081## ##STR00082##
##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087##
##STR00088## where the symbols and indices L, Q, T, X, Y, Z, R,
R.sup.1, and c are defined above and n is 1 or 2.
43. The compound as claimed in claims 38, wherein the symbol M is
Al, Ga, In, Sc, Y, La, Ru, Os, Rh, Ir or Au.
44. The compound as claimed in claims 38, wherein the symbol L is
C.
45. The compound as claimed in claims 38, wherein the symbol Q=O or
S.
46. The compound as claimed in claims 38, wherein the symbol T is
N.
47. The compound as claimed in claims 38, wherein the symbol X is
CR.
48. The compound as claimed in claims 38, wherein the symbol Z is
B, CH, CR.sup.1, COR.sup.1, CF, CCl, CBr, SiR, N, P, PO,
RC(CR.sub.2).sub.3, RC(CR.sub.2CR.sub.2).sub.3,
cis,cis-1,3,5-cyclohexyl, RSi(CR.sub.2).sub.3,
RSi(CR.sub.2CR.sub.2).sub.3, N(CR.sub.2).sub.3, N(C=0).sub.3, or
N(CR.sub.2CR.sub.2).sub.3.
49. The compound as claimed in claims 38, wherein the symbol Y is O
or S.
50. The compound as claimed in claims 38, wherein the symbol R is
H, F, CI, Br, I, CN, a straight-chain or branched or cyclic alkyl
or alkoxy group having from 1 to 6 carbon atoms or an aryl or
heteroaryl group which has from 3 to 8 carbon atoms and may be
substituted by one or more nonaromatic R radicals, in which a
plurality of substituents R, either on the same ring or on the two
different rings, together may in turn form a further mono- or
polycyclic, aliphatic or aromatic ring system.
51. The compound as claimed in claims 38, wherein the polycyclic
ring system optionally formed by the R radical(s) corresponds to
benzene, 1- or 2-naphthalene, 1-, 2- or 9-anthracene, 2-, 3- or
4-pyridine, 2-, 4- or 5-pyrimidine, 2-pyrazine, 3- or 4-25
pyridazine, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinoline, 2- or 3-pyrrole,
3-, 4- or 5-pyrazole, 2-, 4- or 5-imidazole, 2- or 3-thiophene, 2-
or 3-selenophene, 2- or 3-furan, 2-(1,3,4-oxadiazole), indole or
carbazole.
52. A process for preparing the compound as claimed in claim 42,
which comprises reacting the compounds (42) to (82) with metal
alkoxides of the formula (83), with metal ketoketonates of the
formula (84) or metal halides of the formula (85), ##STR00089##
where the symbol R.sup.1 and Hal=F, CI, Br, I.
53. The compound as claimed in claim 31, wherein the compound has a
purity (determined by means of .sup.1H NMR and/or HPLC) is more
than 99%.
54. A conjugated, semiconjugated or nonconjugated polymer or
dendrimer containing one or more compounds of the structure (1) as
claimed in claim 32 or of the compounds (1) to (41) ##STR00090##
##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095##
##STR00096## ##STR00097## ##STR00098## wherein M is Al, Ga, In, Tl,
P, As, Sb, Bi, Sc, Y, La, V, Nb, Ta, Cr, Mo, W, Fe, Ru, Os, Co, Rh,
Ir, Cu, Au, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu; L is
the same or different at each instance and is C, N or P; Q is the
same or different at each instance and is O, S, Se, Te or N; T is
the same or different at each instance and is N, P or C; X is the
same or different at each instance and is CR, N or P; Y is the same
or different at each instance and is NR.sup.1, O, S, Se, Te, SO,
SeO, TeO, SO.sub.2, SeO.sub.2 or TeO.sub.2; Z is B, BR,
B(CR.sub.2).sub.3, B(CR.sub.2CR.sub.2).sub.3, CR, COH, COR.sup.1,
CF, CCl, CBr, C--I, CNR.sup.1.sub.2, RC(CR.sub.2).sub.3,
RC(CR.sub.2CR.sub.2).sub.3, RC(SiR.sub.2).sub.3,
RC(SiR.sub.2CR.sub.2).sub.3, RC(CR.sub.2SiR.sub.2).sub.3,
RC(SiR.sub.2SiR.sub.2).sub.3, cis,cis-1,3,5-cyclohexyl,
1,3,5-(CR.sub.2).sub.3C.sub.6H.sub.3, SiR, SiOH, SiOR.sup.1,
RSi(CR.sub.2).sub.3, RSi(CR.sub.2CR.sub.2).sub.3,
RSi(SiR.sub.2).sub.3, RSi(SiR.sub.2CR.sub.2).sub.3,
RSi(CR.sub.2SiR.sub.2).sub.3, RSi(SiR.sub.2SiR.sub.2).sub.3, N,
N(CR.sub.2).sub.3, N(C.dbd.O).sub.3, N(CR.sub.2CR.sub.2).sub.3, NO,
P, As, Sb, Bi, PO, AsO, SbO, BiO, PSe, AsSE, SbSe, BiSe, PTe, AsTe,
SbTe or BiTe; R is the same or different at each instance and is H,
F, Cl, Br, I, NO.sub.2, CN, a straight-chain or branched or cyclic
alkyl or alkoxy group having from 1 to 20 carbon atoms, in which
one or more nonadjacent CH.sub.2 groups is optionally replaced by
--R.sup.1C.dbd.CR.sup.1--, --C.ident.C--, Si(R.sup.1).sub.2,
Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.1, --O--, --S--, --NR.sup.1-- or --CONR.sup.1--, and
in which one or more hydrogen atoms is optionally replaced by F, or
an aryl or heteroaryl group which has from 1 to 14 carbon atoms and
is optionally substituted by one or more nonaromatic R radicals,
where a plurality of substituents R, both on the same ring and on
the two different rings, together optionally forms a further mono-
or polycyclic, aliphatic or aromatic ring system; R.sup.1 is the
same or different at each instance and is an aliphatic or aromatic
hydrocarbon radical having from 1 to 20 carbon atoms; c is the same
or different at each instance and is 0 or 1 and n is 1 or 2.
55. A conjugated, semiconjugated or nonconjugated polymer or
dendrimer as claimed in claim 54, in which one or more of the R
radicals is a bond to the polymer or dendrimer.
56. The polymer as claimed in claim 54, wherein the polymer is
selected from the group of polyfluorenes, poly-spiro-bifluorenes,
poly-para-phenylenes, polycarbazoles, polyvinylcarbazoles,
polythiophenes, or else from copolymers which have a plurality of
these units.
57. The polymer as claimed in claim 54, wherein the polymer is
soluble in organic solvents.
58. An electronic component comprising at least one polymer or
dendrimer as claimed in claim 54.
59. The electronic component as claimed in claim 58, wherein the
electronic component is an organic light-emitting diode (OLED),
organic integrated circuit (O-IC), organic field-effect transistor
(OFET), organic thin-film transistor (OTFT), organic solar cell
(O-SC) or organic laser diode (O-laser).
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of application Ser. No.
10/548,855 filed on Sep. 9, 2005, which is a National Stage
Application of International Application No. PCT/EP2004/02393 filed
Mar. 9, 2004, which claims priority to German Patent Application
No. 103 10 887.4 filed on Mar. 11, 2003, all of which are
incorporated herein by reference.
[0002] Organometallic compounds, especially compounds of the
d.sup.8 metals, will find use in the near future as active
components (=functional materials) in a series of different types
of applications which can be classed within the electronics
industry in the widest sense. The organic electroluminescent
devices based on organic components (for a general description of
the construction, see U.S. Pat. No. 4,539,507 and U.S. Pat. No.
5,151,629) and their individual components, the organic
light-emitting diodes (OLEDs), have already been introduced onto
the market, as demonstrated by the available car radios having
organic displays from Pioneer. Further products of this type will
shortly be introduced. In spite of all of this, distinct
improvements are still necessary here for these displays to provide
real competition to the currently market-leading liquid crystal
displays (LCDs) or to overtake them.
[0003] A development in this direction is the improvement of
electron transport materials and blue singlet emitters based on
metal chelate complexes, of which aluminum and lanthanum chelate
complexes in particular are of interest here.
[0004] A further development which has emerged in recent years is
the use of organometallic complexes which exhibit phosphorescence
instead of fluorescence [M. A. Baldo, S. Lamansky, P. E. Burrows,
M. E. Thompson, S. R. Forrest, Applied Physics Letters, 1999, 75,
4-6]. For theoretical reasons relating to spin probability, up to
four times the energy efficiency and power efficiency are possible
using organometallic compounds as phosphorescence emitters. Whether
this new development will establish itself depends strongly upon
whether corresponding device compositions can be found which can
also utilize these advantages (triplet emission=phosphorescence
compared to singlet emission=fluorescence) in OLEDs. The essential
conditions for practical use are in particular a long operative
lifetime, a high stability against thermal stress and a low use and
operating voltage, in order to enable mobile applications.
[0005] In both cases, there has to be efficient chemical access to
the corresponding chelate complexes or organometallic compounds.
However, it is of particular interest against the background of the
rarity of the metals in the case of ruthenium, osmium, rhodium,
iridium and gold compounds.
[0006] The literature has to date described two basic designs of
OLEDs which have fluorescence or phosphorescence emitters as
coloring components:
[0007] Type 1 typically has the following layer structure [using
the example of an OLED with phosphorescence emitter: M. E. Thompson
et al., Proceedings of SPIE, 31 Jul.-2 Aug. 2000, San Diego, USA,
Volume 4105, page 119-124]: [0008] 1. Carrier plate=substrate
(typically glass or plastics films). [0009] 2. Transparent anode
(typically indium tin oxide, ITO). [0010] 3. Hole transport layer
(HTL): typically based on triarylamine derivatives. [0011] 4.
Emitter layer (EL): this layer consists either of a fluorescence
emitter or phosphorescence emitter or a matrix material which is
doped with the fluorescence emitter or phosphorescence emitter.
[0012] 5. Electron transport layer (ETL): usually based on
tris(8-hydroxyquinolinato)aluminum(III) (AlQ.sub.3). [0013] 6.
Cathode: here, generally metals, metal combinations or metal alloys
with a low work function are used, for example Al--Li.
[0014] Type 2 typically has the following layer structure [using
the example of an OLED with phosphorescence emitter: T. Tsutsui et
al. Jpn. J. Appl. Phys., 1999, 38, L 1502-L 1504]: [0015] 1.
Carrier plate=substrate (typically glass or plastics films). [0016]
2. Transparent anode (typically indium tin oxide, ITO). [0017] 3.
Hole transport layer (HTL): typically based on triarylamine
derivatives. [0018] 4. Matrix and emitter layer (EL): this layer
consists of a matrix material, for example based on triarylamine
derivatives, which is doped with the fluorescence emitter or
phosphorescence emitter. [0019] 5. Electron transport/hole-blocking
layer (HBL): typically based on nitrogen heterocycles or based on
metal complexes, for example
bis(2-methyl-8-hydroxyquinolinato)(4-phenylphenolato)aluminum(III)
(B--AlQ.sub.3). [0020] 6. Electron transport layer (ETL): usually
based on tris(8-hydroxyquinolinato)aluminum(III) (AlQ.sub.3).
[0021] 7. Cathode: here, generally metals, metal combinations or
metal alloys with a low work function are used, for example Al.
[0022] It is also possible to emit the light through a thin
transparent cathode. These devices are appropriately (depending on
the use) structured, contacted and finally hermetically sealed,
since the lifetime of such devices is generally drastically
shortened in the presence of water and/or air.
[0023] The characteristic data of the above-described OLEDs show
weaknesses including the following: [0024] 1. The operative
lifetime is in most cases still much too short, which is an
obstacle to introduction of OLEDs on the market. [0025] 2. It is
evident from the efficiency-brightness curves that the efficiency
frequently decreases greatly with increasing brightness. This means
that the high brightnesses needed in practice can be achieved only
by means of a high power consumption. However, high power
consumptions require high battery power of portable units (mobile
phones, laptops, etc.). Moreover, the high power consumption, which
is to a large part converted to heat, can lead to thermal damage to
the display.
[0026] In the above-illustrated OLED device, the abovementioned
function materials have been or are being intensively
optimized.
[0027] For some time, (pseudo)octahedral metal complexes in the
widest sense have been used as the ETL (e.g. AlQ.sub.3, see: C. W.
Tang et al., Applied Phys. Lett. 1987, 51(12), 913), HBL (e.g.
B--AlQ.sub.3, see: R. Kwong et al., Applied Physics Letters 2002,
81(1), 162), as the matrix material in the EL (e.g. B--AlQ.sub.3,
see: C. H. Chen et al., Proceedings of SPIE--The International
Society for Optical Engineering 1998, 3421 (Display Technologies
II), 78), as the singlet emitter (e.g. AlQ.sub.3 and other
complexes, see: S. Tokito et al., Synthetic Metals 2000, 111-112,
393) and as the triplet emitter (e.g. Ir(PPy).sub.3, see: WO
00/70655; e.g. Ir(TPy).sub.3 and Ir(BTPy).sub.3, see: S. Okada et
al., Proceedings of the SID, 2002, 52.2, 1360). In addition to the
individual weaknesses specific to each material, the known metal
complexes have general weaknesses which will be presented briefly
below: [0028] 1. Many of the known metal complexes, in particular
those which include main group metals such as aluminum, have a
sometimes considerable hydrolysis sensitivity which can have such
an extent that the metal complex is decomposed noticeably even
after short exposure to air. Others, in contrast, for example the
AlQ.sub.3 used as an electron transport material, tends to add on
water. [0029] The high hygroscopicity of these and similar aluminum
complexes is a crucial practical disadvantage. AlQ.sub.3 which is
synthesized and stored under standard conditions still contains, in
addition to the hydroxyquinoline ligands, one molecule of water per
complex molecule [cf., for example: H. Schmidbaur et al., Z.
Naturforsch. 1991, 46b, 901-911]. This is extremely difficult to
remove. For use in OLEDs, AlQ.sub.3 therefore has to be purified in
a costly and inconvenient manner in complicated, multistage
sublimation processes, and stored and handled thereafter with
exclusion of water in a protective gas atmosphere. Moreover, large
variations in the quality of individual AlQ.sub.3 batches, and also
poor storage stability were found (see: S. Karg, E-MRS Konferenz 30
May 2000-2 Jun. 2000 Strasbourg). [0030] 2. Many of the known metal
complexes have a low thermal stability. In a vacuum deposition of
the metal complexes, this inevitably always leads to the release of
organic pyrolysis products, some of which considerably reduce the
operative lifetime of the OLEDs even in small amounts. [0031] 3.
Virtually all of the metal complexes which have been detailed in
the literature and have to date found use in OLEDs are homoleptic,
(pseudo)octahedral complexes consisting of a central metal
coordinated to three bidentate ligands. Complexes of this design
can occur in two isomeric forms, the meridional and the facial
isomer. Frequently, there is only a slight thermodynamic preference
for one of the two isomers. Under certain conditions, for example a
certain sublimation temperature, this leads to one or the other
isomer or even mixtures of the two occurring. This is not desired,
since the two isomers often differ distinctly in their physical
properties (emission spectrum, electron and hole conduction
properties, etc.), and the properties of an OLED can thus deviate
distinctly from one another even in the event of small changes in
the preparation process. An example thereof are the distinctly
different properties of mer-AlQ.sub.3 and fac-AlQ.sub.3 which
exhibit green and blue photoluminescence respectively (see M.
Coelle, Chemical Communications, 2002, 23, 2908-2909).
[0032] There is therefore a need for alternative compounds which do
not have the abovementioned weaknesses but are in no way inferior
in efficiency and emission color to the known metal complexes.
[0033] It has now been found that, surprisingly, metal complexes of
polypodal ligands display outstanding properties when used as the
ETL, as the HBL, as the matrix material in the EL, as the singlet
emitter and also as the triplet emitter, the particular specific
function being determined by the suitable selection of the metal
and of the suitable accompanying ligand. These compounds form the
subject matter of the present invention. The compounds feature the
following general properties: [0034] 1. In contrast to many known
metal complexes which are subject to partial or complete pyrolytic
decomposition in the course of sublimation, the inventive compounds
feature high thermal stability. When used in appropriate devices,
this stability leads to a distinct increase in the operative
lifetime. [0035] 2. The inventive compounds do not have any
noticeable hydrolysis or hygroscopicity. Storage for several days
or weeks with ingress of air and water vapor does not lead to any
changes in the substances. It was not possible to detect addition
of water to the compounds. This has the advantage that the
substances can be purified, transported, stored and prepared for
use under simpler conditions. [0036] 3. The inventive compounds,
used as the ETL material in the electroluminescent devices, lead to
high efficiencies which are in particular independent of the
current densities used. This enables very good efficiencies even at
high current densities. [0037] 4. The inventive compounds, used as
the HBL material in the electroluminescent devices, lead to high
efficiencies which are in particular independent of the current
densities used. This enables very good efficiencies even at high
current densities, i.e. high brightnesses. Moreover, the inventive
materials are stable toward holes, which is not the case to a
sufficient degree, for example, for other metal complexes, for
example AlQ.sub.3 and analogous compounds (see, for example: Z.
Popovic et al., Proceedings of SPIE, 1999, 3797, 310-315). [0038]
5. The inventive compounds, used in electroluminescent devices as
the EL material in pure form or as the matrix material in
combination with a dopant, lead therein to high efficiencies, the
electroluminescent devices being notable for steep current-voltage
curves and particularly for long operative lifetime. [0039] 6. The
inventive compounds can be prepared with good reproducibility in
reliably high yield and do not have any variation between batches.
[0040] 7. Some of the inventive compounds have excellent solubility
in organic solvents. This allows these materials to be purified
more readily and also makes them processable from solution by
coating or printing techniques. In the customary processing by
evaporation too, this property is advantageous, since the
purification of the units or of the shadow masks used is thus
considerably eased.
[0041] The class of chelate complexes and organometallic compounds
of polypodal ligands which are described in more detail below and
their use as functional materials in electrooptical components is
novel and has to date not been described in the literature, but
their efficient preparation and availability as pure materials is
of great significance for this purpose.
[0042] The present invention thus provides metal complexes of the
structure 1
##STR00001##
containing at least one metal Met coordinated to a polypodal ligand
Lig of the structure 2,
##STR00002##
where V is a bridging unit, characterized in that it contains from
1 to 80 atoms and the three part-ligands L1, L2 and L3 which may be
the same or different at each instance are covalently bonded to one
another, and where the three part-ligands L1, L2 and L3 satisfy the
structure 3
##STR00003##
where Cy1 and Cy2 are the same or different at each instance and
correspond to substituted or unsubstituted, saturated, unsaturated
or aromatic homo- or heterocycles or part-homo- or
part-heterocycles of a fused system, which are each bonded
ionically, covalently or coordinatively to the metal via a ring
atom or via an atom bonded exocyclically to the homo- or
heterocycle.
[0043] The bridging unit V has from 1 to 80 atoms from main group
III, IV and/or V of the elements of the periodic table. These form
the basic skeleton of the bridging unit.
[0044] The zig-zag line symbol selected above describes here the
linkage of Cy1 to Cy2 only in general terms. A more detailed
description of the possible linkages of the cycles is given
below.
[0045] The homo- or heterocycles Cy1 and Cy2 may be linked via a
single bond. Moreover, the part-homo- or part-heterocycles Cy1 and
Cy2 may be linked via a common edge. Furthermore, in addition to
the linkage via a single bond or a common edge, they may be linked
to one another via substituents on the homo- or heterocycles Cy1
and Cy2 or the part-homo- or part-heterocycles, and thus form a
polycyclic, aromatic or aliphatic ring system.
[0046] The linkages possible in principle will be shown here by way
of example using the example of a benzene ring (Cy1) and of a
pyridine (Cy2) (see FIG. 1) without any intention thus to restrict
the multitude of all possible linkages.
##STR00004##
[0047] Preference is given to inventive compounds of the structure
1, characterized in that they are uncharged, i.e. are externally
electrically neutral.
[0048] Preference is given to inventive compounds of the structure
1, characterized in that at least one of the part-ligands L1, L2
and L3, preferably at least two of the part-ligands L1, L2 and L3,
and more preferably all three part-ligands L1, L2 and L3 are singly
negatively charged.
[0049] Preference is given to inventive compounds of the structure
1, characterized in that L1=L2=L3.
[0050] Preference is likewise given to inventive compounds of the
structure 1, characterized in that L1.noteq.L2.
[0051] Preference is further given to inventive compounds of the
structure 1, characterized in that Cy1 is different from Cy2.
[0052] Preference is given to inventive compounds of the structure
1, characterized in that the linking unit V contains, as the
linking atom, an element of main group 3, 4 or 5, or a 3- to
6-membered homo- or heterocycle.
[0053] Preference is given to inventive compounds of the structure
1, characterized in that the polypodal ligand Lig of the structure
4 generates facial coordination geometry on the metal Met.
##STR00005##
[0054] Preference is likewise given to inventive compounds of the
structure 1, characterized in that the polypodal ligand Lig of the
structure 5 generates meridional coordination geometry on the metal
Met.
##STR00006##
[0055] In the context of this application, facial and meridional
coordination describe the environment of the metal Met with the six
donor atoms. Facial coordination is present when three identical
donor atoms occupy a triangular surface in the (pseudo)octahedral
coordination polyhedron, and three identical donor atoms other than
the first three occupy another triangular surface in the
(pseudo)octahedral coordination polyhedron. Analogously, a
meridional coordination is understood to be one in which three
identical donor atoms occupy one meridian in the (pseudo)octahedral
coordination polyhedron, and three identical donor atoms other than
the first three occupy the other meridian in the (pseudo)octahedral
coordination polyhedron. This will be shown below by way of example
with reference to an example of a coordination of three nitrogen
donor atoms and three carbon donor atoms (see FIG. 2). Since this
description relates to donor atoms and not to the cycles Cy1 and
Cy2 which provide these donor atoms, the three cycles Cy1 and the
three cycles Cy2 may be the same or different at each instance and
nevertheless correspond to a facial or meridional coordination in
the context of this application.
[0056] Identical donor atoms are understood to be those which
consist of the same elements (e.g. nitrogen), irrespective of
whether these elements are incorporated within different structures
or cyclic structures.
##STR00007##
[0057] Preference is given in particular to metal complexes
according to the compounds (1) to (8) with facial coordination
geometry on the metal according to Scheme 1
##STR00008## ##STR00009##
where the symbols and indices are each defined as follows: [0058] M
is Al, Ga, In, Tl, P, As, Sb, Bi, Sc, Y, La, V, Nb, Ta, Cr, Mo, W,
Fe, Ru, Os, Co, Rh, Ir, Cu, Au, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er,
Tm, Yb, Lu; [0059] L is the same or different at each instance and
is C, N, P; [0060] Q is the same or different at each instance and
is O, S, Se, Te, N; [0061] T is the same or different at each
instance and is N, P, C; [0062] X is the same or different at each
instance and is CR, N, P; [0063] Y is the same or different at each
instance and is NR.sup.1, O, S, Se, Te, SO, SeO, TeO, SO.sub.2,
SeO.sub.2, TeO.sub.2; [0064] Z is B, BR, B(CR.sub.2).sub.3,
B(CR.sub.2CR.sub.2).sub.3, CR, COH, COR.sup.1, CF, CCl, CBr, C--I,
CNR.sup.1.sub.2, RC(CR.sub.2).sub.3, RC(CR.sub.2CR.sub.2).sub.3,
RC(SiR.sub.2).sub.3, RC(SiR.sub.2CR.sub.2).sub.3,
RC(CR.sub.2SiR.sub.2).sub.3, RC(SiR.sub.2SiR.sub.2).sub.3,
cis,cis-1,3,5-cyclohexyl, 1,3,5-(CR.sub.2).sub.3C.sub.6H.sub.3,
SiR, SiOH, SiOR.sup.1, RSi(CR.sub.2).sub.3,
RSi(CR.sub.2CR.sub.2).sub.3, RSi(SiR.sub.2).sub.3,
RSi(SiR.sub.2CR.sub.2).sub.3, RSi(CR.sub.2SiR.sub.2).sub.3,
RSi(SiR.sub.2SiR.sub.2).sub.3, N, N(CR.sub.2).sub.3,
N(C.dbd.O).sub.3, N(CR.sub.2CR.sub.2).sub.3, NO, P, As, Sb, Bi, PO,
AsO, SbO, BiO, PSe, AsSe, SbSe, BiSe, PTe, AsTe, SbTe, BiTe; [0065]
R is the same or different at each instance and is H, F, Cl, Br, I,
NO.sub.2, CN, a straight-chain or branched or cyclic alkyl or
alkoxy group having from 1 to 20 carbon atoms, in which one or more
nonadjacent CH.sub.2 groups may be replaced by
--R.sup.1C.dbd.CR.sup.1--, --C.ident.C--, Si(R.sup.1).sub.2,
Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.1, --O--, --S--, --NR.sup.1-- or --CONR.sup.1--, and
in which one or more hydrogen atoms may be replaced by F, or an
aryl or heteroaryl group which has from 1 to 14 carbon atoms and
may be substituted by one or more nonaromatic R radicals, where a
plurality of substituents R, both on the same ring and on the two
different rings, together may in turn form a further mono- or
polycyclic, aliphatic or aromatic ring system; [0066] R.sup.1 is
the same or different at each instance and is an aliphatic or
aromatic hydrocarbon radical having from 1 to 20 carbon atoms;
[0067] c is the same or different at each instance and is 0 or
1.
[0068] Furthermore, preference is likewise given to the compounds
(9) to (12) with meridional coordination geometry on the metal
according to Scheme 2
##STR00010##
where the symbols and indices M, L, Q, T, X, Y, Z, R, R.sup.1 and c
are each as defined in Scheme 1, and where: n is 1 or 2.
[0069] The invention further likewise provides compounds which
simultaneously have part-ligands of the type as in compounds (1),
(2), (3) and/or (4), i.e. mixed ligand systems. These are described
by the formulae (13) to (30) according to Scheme 3:
##STR00011## ##STR00012## ##STR00013##
where the symbols and indices M, L, Q, T, X, Y, Z, R, R.sup.1, c
and n are each as defined in Scheme 1 and 2.
[0070] The invention further likewise provides the compounds (31)
to (41) which contain fused aromatic ligand systems according to
Scheme 4:
##STR00014## ##STR00015##
where the symbols and indices M, L, Q, T, X, Y, Z, R, R.sup.1, c
and n are each as defined in Scheme 1 and 2.
[0071] Preference is given to inventive compounds (1) to (41) in
which the symbol M=Al, Ga, In, Sc, Y, La, Ru, Os, Rh, Ir, Au.
[0072] Preference is likewise given to inventive compounds (1) to
(41) in which the symbol L=C, N.
[0073] Preference is likewise given to inventive compounds (1) to
(41) in which the symbol Q=O, S.
[0074] Preference is likewise given to inventive compounds (1) to
(41) in which the symbol T=N.
[0075] Preference is likewise given to inventive compounds (1) to
(41) in which the symbol X=CR, N.
[0076] Preference is likewise given to inventive compounds (1) to
(41) in which the symbol Z=B, CH, CR.sup.1, COR.sup.1, CF, CCl,
CBr, SiR, N, P, PO, RC(CR.sub.2).sub.3, RC(CR.sub.2CR.sub.2).sub.3,
cis,cis-1,3,5-cyclohexyl, RSi(CR.sub.2).sub.3,
RSi(CR.sub.2CR.sub.2).sub.3, N(CR.sub.2).sub.3, N(C.dbd.O).sub.3,
N(CR.sub.2CR.sub.2).sub.3.
[0077] Preference is likewise given to inventive compounds (1) to
(41) in which the symbol Y=O, S.
[0078] Preference is likewise given to inventive compounds (1) to
(41) in which the symbol R represents H, F, Cl, Br, I, CN, a
straight-chain or branched or cyclic alkyl or alkoxy group having
from 1 to 6 carbon atoms or an aryl or heteroaryl group which has
from 3 to 8 carbon atoms and may be substituted by one or more
nonaromatic R radicals, in which a plurality of substituents R,
either on the same ring or on the two different rings, together may
in turn form a further mono- or polycyclic, aliphatic or aromatic
ring system.
[0079] When ring systems are formed by the R radicals in the
compounds (1) to (41), they are preferably benzene, 1- or
2-naphthalene, 1-, 2- or 9-anthracene, 2-, 3- or 4-pyridine, 2-, 4-
or 5-pyrimidine, 2-pyrazine, 3- or 4-pyridazine, 2-, 3-, 4-, 5-,
6-, 7- or 8-quinoline, 2- or 3-pyrrole, 3-, 4- or 5-pyrazole, 2-,
4- or 5-imidazole, 2- or 3-thiophene, 2- or 3-selenophene, 2- or
3-furan, 2-(1,3,4-oxadiazole), indole or carbazole.
[0080] The present invention likewise provides the polypodal
ligands according to compounds (42) to (82), according to Scheme
5:
##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020##
##STR00021## ##STR00022## ##STR00023## ##STR00024##
where the symbols and indices Q, L, T, X, Y, Z, R, R.sup.1, c, n
are each as defined in Scheme 1 and 2.
[0081] The inventive compounds (1) to (41) can in principle be
prepared by various processes, although the process described below
has been found to be particularly suitable.
[0082] The present invention therefore further provides a process
for preparing the compounds (1) to (41) by reacting the polypodal
ligands of the compounds (42) to (82) with metal alkoxides of the
formula (83), with metal ketoketonates of the formula (84) and
metal halides of the formula (85),
##STR00025##
where the symbol R.sup.1 is as defined in Scheme 1 and Hal=F, Cl,
Br, I.
[0083] This process allows the complexes to be obtained readily in
high purity, preferably in a purity of >99%, by .sup.1H NMR or
HPLC.
[0084] The synthetic methods illustrated here allow examples
including the examples of compounds (1) to (41) shown below to be
prepared.
##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030##
##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035##
##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040##
##STR00041## ##STR00042## ##STR00043## ##STR00044##
##STR00045##
[0085] The above-described inventive compounds, for example
compounds according to Examples 7, 14, 26, 27, 37, 38, 39 and 41,
may find use, for example, as comonomers to obtain corresponding
conjugated, semiconjugated or else nonconjugated polymers, or else
as the core of dendrimers, for example compounds according to
Examples 14 and 26. The appropriate polymerization is effected
preferably via the halogen functionality.
[0086] For instance, they can be polymerized, inter alia, into
soluble polyfluorenes (for example according to EP-A-842208 or WO
00/22026), poly-spiro-bifluorenes (for example according to
EP-A-707020 or EP-A-894107), poly-para-phenylenes (for example
according to WO 92/18552), polycarbazoles (for example according to
the applications DE 10304819.7 and DE 10328627.6),
polyvinylcarbazoles or else polythiophenes (for example according
to EP-A-1028136), or else copolymers of a plurality of these
units.
[0087] The invention thus further provides conjugated,
semiconjugated and nonconjugated polymers or dendrimers containing
one or more compounds of the formula (1) to (41), in which one or
more of the above-defined R radicals is a bond to the polymer or
dendrimer.
[0088] In addition, the inventive metal complexes may of course
also be functionalized further and thus be converted to extended
metal complexes. Here, mention may be made as an example of the
functionalization with arylboronic acids according to SUZUKI or
with amines according to HARTWIG-BUCHWALD.
[0089] The above-described inventive compounds, polymers,
dendrimers or, as described above, compounds which have been
further functionalized find use as active components in electronic
components, for example organic light-emitting diodes (OLEDs),
organic integrated circuits (O-ICs), organic field-effect
transistors (OFETs), organic thin-film transistors (OTFTs), organic
solar cells (O-SCs) or organic laser diodes (O-lasers).
[0090] Active components are, for example, charge injection or
charge transport materials, charge blocking materials and emission
materials. For this function, the inventive compounds exhibit
particularly good properties, as has already been illustrated above
and will be further explained below in more detail.
[0091] The invention thus further provides for the use of these
compounds in electronic components.
[0092] The invention further provides electronic components, for
example organic integrated circuits (O-ICs), organic field-effect
transistors (OFETs), organic thin-film transistors (OTFTs), organic
solar cells (O-SCs) or organic laser diodes (O-lasers), but in
particular organic light-emitting diodes (OLEDs) which comprise one
or more of the inventive compounds, polymers or dendrimers.
[0093] The present invention is illustrated in detail by the
examples which follow of charge transport and hole blocker
materials, without any intention to restrict it thereto. Without
inventive activity, those skilled in the art can use the remarks to
prepare further inventive complexes, for example emission
materials, or employ the process according to the invention.
EXAMPLES
Synthesis of Homoleptic Aluminum, Iron and Lanthanum Chelate
Complexes with Hexapodal Ligands
[0094] Unless stated otherwise, the syntheses which follow were
carried out under a protective gas atmosphere in dried solvents.
The reactants were purchased from ALDRICH or ABCR
[2-methoxybenzeneboronic acid, 2-bromo-4-fluorophenol,
2-bromo-5-fluorophenol, potassium fluoride (spray-dried),
diethylaminosulfur trifluoride (DAST), tri-tert-butylphosphine,
palladium(II) acetate, pyridinium hydrochloride, aluminum
triisopropoxide, 10% by weight solution of
tris(2-methoxyethanolato)lanthanum(III) in 2-methoxyethanol].
Tris(2-bromo-6-pyridyl)phosphine and
tris(2-bromo-6-pyridyl)methanol were prepared as described in WO
98/22148.
Example 1
Tris(2-bromo-6-pyridyl)phosphine oxide
##STR00046##
[0096] A suspension, heated to boiling, of 50.2 g (100.0 mmol) of
tris(2-bromo-6-pyridyl)phosphine in 500 ml of chloroform was
admixed with intensive stirring dropwise with a mixture of 11 ml of
35% by weight H.sub.2O.sub.2 and 50 ml of water, which afforded a
clear solution. After stirring under reflux for 5 h, the solution
was allowed to cool to room temperature. The solution was washed
with 500 ml of water, and the organic phase was removed and
concentrated to 50 ml under reduced pressure. After standing for 2
h, the precipitated crystals were filtered off, washed three times
with 100 ml of n-hexane and then dried at 70.degree. C. under
reduced pressure. The yield at a purity of 99.0% was 47.1 g
(90.9%).
[0097] .sup.1H NMR (CDCl.sub.3): .delta. [ppm]=8.14 (ddd,
.sup.3J.sub.HP=5.4 Hz, .sup.3J.sub.HH=7.8 Hz, .sup.4J.sub.HH=1.0
Hz, 3H, H-3), 7.69 (ddd, .sup.4J.sub.HP=4.6 Hz, .sup.3J.sub.HH=7.9
Hz, .sup.3J.sub.HH=7.9 Hz, 3H, H-4), 7.61 (ddd, .sup.5J.sub.HP=2.1
Hz, .sup.3J.sub.HH=7.9 Hz, .sup.4J.sub.HH=1.0 Hz, 3H, H-5).
[0098] .sup.31P{.sup.1H} NMR (CDCl.sub.3): .delta. [ppm]=11.8
(s).
Example 2
Tris(6-(2-methoxyphenyl)-2-pyridyl)phosphine oxide
##STR00047##
[0100] An efficiently stirred suspension of 38.8 g (75.0 mmol) of
tris(2-bromo-6-pyridyl)phosphine oxide, 51.3 g (337.5 mmol) of
2-methoxybenzeneboronic acid and 43.1 g (742.5 mmol) of potassium
fluoride in 750 ml of anhydrous THF was admixed with 593 mg (2.93
mmol) of tri-tert-butylphosphine and then with 505 mg (2.25 mmol)
of palladium(II) acetate, and subsequently heated under reflux for
16 h. After cooling, the reaction mixture was admixed with 1500 ml
of ethyl acetate and 1000 ml of water. The organic phase was
removed, washed twice with 500 ml of water and once with 500 ml of
sat. sodium chloride solution, and subsequently dried over
magnesium sulfate. After the organic phase had been concentrated
under reduced pressure (end pressure 1 mbar, temperature 90.degree.
C.), 44.3 g (98.5%) of a pale yellow highly viscous oil remained,
which was reacted further without purification.
[0101] .sup.1H NMR (CDCl.sub.3): .delta. [ppm]=8.14 (ddd, 3H), 8.02
(ddd, 3H), 7.85 (dd, 3H), 7.76 (ddd, 3H), 7.30 (ddd, 3H), 6.94 (dd,
3H), 6.87 (ddd, 3H), 3.10 (s, 9H CH.sub.3).
[0102] .sup.31P{.sup.1H} NMR (CDCl.sub.3): .delta. [ppm]=14.0
(s).
Example 3
Tris(6-(2-hydroxyphenyl)-2-pyridyl)phosphine oxide, (PPL-01)
##STR00048##
[0104] A mixture of 30.0 g (50 mmol) of
tris(6-(2-methoxyphenyl)-2-pyridyl)phosphine oxide and 104.0 g (900
mmol) of pyridinium hydrochloride was stirred at 130.degree. C. for
12 h. After the melt had been cooled to 80.degree. C., it was
admixed with 300 ml of water and then with a solution of 44.9 g
(800 mmol) of potassium hydroxide in 100 ml of water. The aqueous
phase was extracted three times with 500 ml of dichloromethane. The
combined organic phases were washed three times with 500 ml of
water. After the organic phase had been dried over magnesium
sulfate and the dichloromethane had been removed, the oily residue
was taken up in 100 ml of methyl tert-butyl ether and admixed with
100 ml of n-heptane. After standing for 12 h, the colorless
crystals were filtered off with suction and recrystallized from
methyl tert-butyl ether/n-heptane. The yield was 10.9 g (39.1%) at
a purity of greater than 99.0% by .sup.1H NMR.
[0105] .sup.1H NMR (CDCl.sub.3): .delta. [ppm]=14.33 (s, 3H, OH),
8.45 (m, 3H), 8.13 (m, 3H), 7.88 (m, 3H), 7.61 (m, 3H), 7.23 (m,
3H), 7.01 (m, 3H), 6.90 (m, 3H).
[0106] .sup.31P{.sup.1H} NMR (CDCl.sub.3): .delta. [ppm]=10.3
(s).
Example 4
Tris(2-bromo-6-pyridyl)fluoromethane
##STR00049##
[0108] A solution of 50.0 g (100 mmol) of
tris(2-bromo-6-pyridyl)methanol in 750 ml of dichloromethane was
admixed with good stirring dropwise with 47.3 ml (400 mmol) of
diethylaminosulfur trifluoride. Subsequently, the reaction mixture
was heated under reflux for 30 min, then cooled to 5.degree. C.,
and admixed with good stirring (highly exothermic!!!) with 300 ml
of water and then with a solution of 64.0 g (1600 mmol) of sodium
hydroxide in 600 ml of water (highly exothermic!!!). The organic
phase was removed, the aqueous phase was washed twice with 200 ml
of dichloromethane, and the combined organic phases were dried over
calcium chloride and subsequently freed of dichloromethane. The
remaining red-brown crystal slurry was taken up in 100 ml of
methanol and filtered off. After washing with methanol, the
colorless to beige crystals were dried under reduced pressure. The
yield was 47.4 g (91.3%) at a purity of greater than 99.0% by
.sup.1H NMR.
[0109] .sup.1H NMR (CDCl.sub.3): .delta. [ppm]=7.58 (ddd,
.sup.3J.sub.HH=7.7 Hz, .sup.3J.sub.HH=7.7 Hz, .sup.5J.sub.FH=0.7
Hz, 1H, H-4), 7.53 (dd, .sup.3J.sub.HH=7.7 Hz, .sup.4J.sub.HH=0.7
Hz, 1H, H-3), 7.45 (ddd, .sup.3J.sub.HH=7.7 Hz, .sup.4J.sub.HH=0.7
Hz, .sup.4J.sub.FH=0.9 Hz, 1H, H-5).
[0110] .sup.19F{.sup.1H} NMR (CDCl.sub.3): .delta. [ppm]=-146.2
(s).
Example 5
2-Bromo-4-fluoro-1-(tetrahydropyran-2-yloxy)benzene
##STR00050##
[0112] A mixture of 478.0 ml (5.24 mol) of 3,4-dihydropyran and 750
ml of dichloromethane was admixed with 65.4 g (260 mmol) of
pyridinium p-toluenesulfonate. Subsequently, a solution of 500.0 g
(2.62 mmol) of 2-bromo-4-fluorophenol in 500 ml of dichloromethane
was added dropwise. After stirring for 24 h, the reaction mixture
was admixed with a solution of 50 g of potassium carbonate in 500
ml of water, and then with 500 ml of saturated sodium chloride
solution. The organic phase was removed, dried over potassium
carbonate and, after freeing it of the solvent and potassium
carbonate, fractionally distilled (approx. 1 mbar, top temperature
from 79 to 82.degree. C.) by means of a Vigreux column (40 cm). The
product was obtained as a colorless, low-viscosity oil. The yield
was 520.5 g (72.2%) at a purity of greater than 98.0% by .sup.1H
NMR.
[0113] .sup.1H NMR (CDCl.sub.3): .delta. [ppm]=7.27 (dd,
.sup.3J.sub.FH=8.0 Hz, .sup.4J.sub.HH=3.0 Hz, 1H, H-3), 7.10 (dd,
.sup.3J.sub.HH=9.7 Hz, .sup.4J.sub.FH=5.0 Hz, 1H, H-6), 6.93 (ddd,
.sup.3J.sub.HH=9.7 Hz, .sup.3J.sub.FH=8.0 Hz, .sup.4J.sub.HH=3.2
Hz, 1H, H-5), 5.39 (m, 1H, CH), 3.88 (m, 1H, CH.sub.2O), 3.59 (m,
1H, CH.sub.2O), 2.12-1.53 (m, 6H, CH.sub.2).
[0114] .sup.19F{.sup.1H} NMR (CDCl.sub.3): .delta. [ppm]=-121.1
(s).
Example 6
5-Fluoro-2-(tetrahydropyran-2-yloxy)benzeneboronic acid
##STR00051##
[0116] 48.6 g (2.00 mol) of magnesium and 510 g (1.85 mol) of
2-bromo-4-fluoro-1-(tetrahydropyran-2-yloxy)benzene in 1250 ml of
THF were used to prepare a Grignard reagent. This Grignard reagent
was slowly added dropwise at -78.degree. C. to a mixture of 241.6
ml (2.00 mol) of trimethyl borate in 500 ml of THF. On completion
of addition, the reaction mixture was allowed to warm to room
temperature and was hydrolyzed by addition of 100 ml of saturated
potassium carbonate solution and 1000 ml of water. The organic
phase was washed with saturated sodium chloride solution
(1.times.500 ml) and subsequently concentrated to dryness. The
yield was 428.2 g (1.78 mol), and the product was obtained as a
waxy solid which contained varying proportions of boronic anhydride
and borinic acids and was used in the following stage without
further purification.
Example 7
Tris(6-(5-fluoro-2-hydroxyphenyl)-2-pyridyl]fluoromethane,
(PPL-02)
##STR00052##
[0118] Procedure of the Suzuki coupling analogous to Example 2, for
which 51.9 g (100 mmol) of tris(2-bromo-6-pyridyl)fluoromethane
(Example 4), 108.0 g (450 mmol) of
5-fluoro-2-(tetrahydropyran-2-yloxy)benzeneboronic acid (Example
6), 57.5 g (990 mmol) of potassium fluoride, 1.35 g (6 mmol) of
palladium(II) acetate and 1.8 ml (8 mmol) of
tri-tert-butylphosphine in 1000 ml of THF were used.
[0119] After 6 h under reflux, the reaction mixture was freed of
the THF on a rotary evaporator, and the slurrylike residue was
taken up in 1000 ml of methanol, admixed with a mixture of 300 ml
of water and 55 ml of 5N HCl and subsequently stirred at 50.degree.
C. for a further 3 h. The resulting crystal slurry was filtered off
with suction (P3), washed with methanol and dried.
Recrystallization from a little chloroform with addition of
methanol gave 53.2 g (89.0%) of the product in the form of
colorless crystals having a purity of greater than 99.0% by .sup.1H
NMR.
[0120] .sup.1H NMR (CDCl.sub.3): .delta. [ppm]=12.34 (s, 3H, OH),
7.99 (dd, .sup.3J.sub.HH=8.4 Hz, .sup.3J.sub.HH=8.4 Hz, 3H,
H-4-Py), 7.86 (d, .sup.3J.sub.HH=8.4 Hz, 3H, H-5-Py), 7.79 (d,
.sup.3J.sub.HH=8.4 Hz, 3H, H-3-Py), 7.45 (dd, .sup.3J.sub.HH=9.4
Hz, .sup.4J.sub.FH=3.0 Hz, 3H, H-3), 6.95 (ddd, .sup.3J.sub.HH=9.4
Hz, .sup.3J.sub.FH=8.0 Hz, .sup.4J.sub.HH=3.0 Hz, 3H, H-4), 6.76
(dd, .sup.3J.sub.FH=9.0 Hz, .sup.4J.sub.HH=3.0 Hz, 3H, H-6).
[0121] .sup.19F{.sup.1H} NMR (CDCl.sub.3): .delta. [ppm]=-144.9 (s,
1F), -125.9 (s, 3F).
Example 8
2-Bromo-5-fluoro-1-(tetrahydropyran-2-yloxy)benzene
##STR00053##
[0123] Procedure analogous to Example 5. Use of 478.0 ml (5.24 mol)
of 3,4-dihydropyran, 65.4 g (260 mmol) of pyridinium
p-toluenesulfonate and 500.0 g (2.62 mmol) of
2-bromo-5-fluorophenol. The yield was 562.2 g (78.0%) at a purity
of greater than 98.0% by .sup.1H NMR.
[0124] .sup.1H NMR (CDCl.sub.3): .delta. [ppm]=7.45 (dd,
.sup.3J.sub.HH=9.1 Hz, .sup.4J.sub.FH=6.4 Hz, 1H, H-3), 6.92 (dd,
.sup.3J.sub.FH=10.7 Hz, .sup.4J.sub.FH=2.7 Hz, 1H, H-6), 6.60 (ddd,
.sup.3J.sub.HH=9.1 Hz, .sup.3J.sub.FH=8.7 Hz, .sup.4J.sub.HH=2.7
Hz, 1H, H-4), 5.46 (m, 1H, CH), 3.84 (m, 1H, CH.sub.2O), 3.62 (m,
1H, CH.sub.2O), 2.14-1.56 (m, 6H, CH.sub.2).
[0125] .sup.19F{.sup.1H} NMR (CDCl.sub.3): .delta. [ppm]=-112.7
(s).
Example 9
4-Fluoro-2-(tetrahydropyran-2-yloxy)benzeneboronic acid
##STR00054##
[0127] Procedure analogous to Example 6. Use of 48.6 g (2.00 mol)
of magnesium, 510 g (1.85 mol) of
2-bromo-5-fluoro-1-(tetrahydropyran-2-yloxy)benzene and 241.6 ml
(2.00 mol) of trimethyl borate. The yield was 434.5 g (1.81 mol),
and the product was obtained as a waxy solid which contained
varying proportions of boronic anhydrides and borinic acids and was
used in the following stage without further purification.
Example 10
Tris(6-(4-fluoro-2-hydroxyphenyl)-2-pyridyl)fluoromethane,
(PPL-03)
##STR00055##
[0129] Procedure analogous to Example 7. Use of 51.9 g (100 mmol)
of tris(2-bromo-6-pyridyl)fluoromethane (Example 4), 108.0 g (450
mmol) of 4-fluoro-2-(tetrahydropyran-2-yloxy)benzeneboronic acid
(Example 9), 57.5 g (990 mmol) of potassium fluoride, 1.35 g (6
mmol) of palladium(II) acetate and 1.8 ml (8 mmol) of
tri-tert-butylphosphine. The yield was 56.9 g (95.5%) of the
product in the form of colorless crystals having a purity of
greater than 99.0% by .sup.1H NMR.
[0130] .sup.1H NMR (CDCl.sub.3): .delta. [ppm]=13.01 (s, 3H, OH),
7.96 (dd, .sup.3J.sub.HH=8.2 Hz, .sup.3J.sub.HH=8.2 Hz, 3H,
H-4-Py), 7.86 (d, .sup.3J.sub.HH=8.2 Hz, 3H, H-5-Py), 7.75 (dd,
.sup.3J.sub.HH=9.4 Hz, .sup.4J.sub.FH=6.4 Hz, 3H, H-6), 7.52 (d,
.sup.3J.sub.HH=8.2 Hz, 3H, H-3-Py), 6.59 (ddd, .sup.3J.sub.HH=9.4
Hz, .sup.3J.sub.FH=8.0 Hz, .sup.4J.sub.HH=2.7 Hz, 3H, H-5), 6.51
(dd, .sup.3J.sub.FH=10.7 Hz, .sup.4J.sub.HH=2.7 Hz, 3H, H-3).
[0131] .sup.19F{.sup.1H} NMR (CDCl.sub.3): .delta. [ppm]=-144.7 (s,
1F), -108.6 (s, 3F).
Example 11
Mono[tris(6-(2-oxyphenyl)-2-pyridyl)phosphinoxido]aluminum(III);
Al-PPL-01
##STR00056##
[0133] A solution of 5.58 g (10 mmol) of
tris(6-(2-hydroxyphenyl)-2-pyridyl)phosphine oxide (Example 3) in
100 ml of toluene was admixed at 80.degree. C. over 30 min with a
solution of 2.04 g (10 mmol) of tris(isopropanolato)aluminum(III)
in 50 ml of toluene. The reaction mixture was heated under reflux
for a further 3 h. After cooling to room temperature, the colorless
precipitate was filtered off with suction, washed with toluene
(1.times.25 ml) and dried. Repeated recrystallization from DMSO
gave 5.03 g (86.5%) of the complex at a purity of 99.8% by
HPLC.
[0134] MS (FAB): m/e=582.
Example 12
Mono[tris(6-(2-oxyphenyl)-2-pyridyl)phosphinoxido]lanthanum(III);
La-PPL-01
##STR00057##
[0136] A solution of 5.58 g (10 mmol) of
tris(6-(2-hydroxyphenyl)-2-pyridyl)phosphine oxide (Example 3) in
100 ml of toluene was admixed at 80.degree. C. over 30 min with
36.4 ml (10 mmol) of a 10% by weight solution of
tris(2-methoxyethanolato)lanthanum(III) in 2-methoxyethanol. The
reaction mixture was heated under reflux for a further 3 h. After
cooling to room temperature, the colorless precipitate was filtered
off with suction, washed with toluene (1.times.25 ml) and dried.
Repeated recrystallization from DMSO gave 5.68 g (81.7%) of the
complex at a purity of 99.8% by HPLC.
[0137] MS (FAB): m/e=693.
Example 13
Mono[tris(6-(5-fluoro-2-oxyphenyl)-2-pyridyl)fluoromethanato]aluminum(III)-
; Al-PPL-02
##STR00058##
[0139] A solution of 5.96 g (10 mmol) of
tris(6-(5-fluoro-2-hydroxyphenyl)-2-pyridyl)fluoromethane (Example
7) in 200 ml of THF was admixed first with 19.4 ml (240 mmol) of
pyridine and then, dropwise at room temperature over 30 min, with a
solution of 20 ml of 0.5 N aluminum chloride solution in ethanol.
The reaction mixture was heated to reflux for a further 3 h. After
cooling to room temperature, the colorless precipitate was filtered
off with suction, washed with THF (3.times.50 ml) and ethanol
(3.times.50 ml) and then dried. Repeated recrystallization from
DMSO (200 ml) gave 5.59 g (90.3%) of the pale yellow complex at a
purity of 99.9% by .sup.1H NMR.
[0140] .sup.1H NMR (DMSO-d6): .delta. [ppm]=8.23 (dd,
.sup.3J.sub.HH=8.0 Hz, .sup.3J.sub.HH=8.0 Hz, 3H, H-4-Py), 8.17 (d,
.sup.3J.sub.HH=8.0 Hz, 3H, H-5-Py), 7.99 (dd, .sup.3J.sub.HH=8.0
Hz, .sup.4J.sub.FH=3.4 Hz, 3H, H-3-Py), 7.69 (dd,
.sup.3J.sub.HH=9.0 Hz, .sup.4J.sub.FH=3.0 Hz, 3H, H-3), 7.03 (ddd,
.sup.3J.sub.HH=9.0 Hz, .sup.3J.sub.FH=9.0 Hz, .sup.4J.sub.HH=3.4
Hz, 3H, H-4), 6.19 (dd, .sup.3J.sub.FH=9.0 Hz, .sup.4J.sub.HH=3.4
Hz, 3H, H-6).
[0141] .sup.19F{.sup.1H} NMR (DMSO-d6): .delta. [ppm]=-177.5 (s,
1F), -128.6 (s, 3F).
[0142] T.sub.g: 178.degree. C.
Example 14
Mono[tris(6-(5-fluoro-2-oxyphenyl)-2-pyridyl)fluoromethanato]iron(III);
Fe-PPL2
##STR00059##
[0144] Procedure analogous to Example 13. Use of 5.96 g (10 mmol)
of tris(6-(5-fluoro-2-hydroxyphenyl)-2-pyridyl)fluoromethane
(Example 10) and 20 ml of a 0.5N iron(III) chloride.6H.sub.2O
solution in ethanol. Repeated recrystallization from DMSO (200 ml)
with addition of 100 ml of ethanol after cooling of the solution to
120.degree. C. gave 5.39 g (83.1%) of the black complex.
[0145] MS (FAB): m/e=648.
Example 15
Mono[tris(6-(4-fluoro-2-oxyphenyl)-2-pyridyl)fluoromethanato]aluminum(III)-
; Al-PPL3
##STR00060##
[0147] Procedure analogous to Example 13. Use of 5.96 g (10 mmol)
of tris(6-(4-fluoro-2-hydroxyphenyl)-2-pyridyl)fluoromethane
(Example 10) and 20 ml of a 0.5N aluminum chloride solution in
ethanol. Repeated recrystallization from DMSO (200 ml) gave 5.32 g
(86.0%) of the pale yellow complex at a purity of 99.9% by .sup.1H
NMR.
[0148] .sup.1H NMR (DMSO-d6): .delta. [ppm]=8.24 (dd,
.sup.3J.sub.HH=8.0 Hz, .sup.3J.sub.HH=8.0 Hz, 3H, H-4-Py), 8.15 (d,
.sup.3J.sub.HH=8.0 Hz, 3H, H-5-Py), 7.97 (dd, .sup.3J.sub.HH=8.0
Hz, .sup.4J.sub.FH=3.4 Hz, 3H, H-3-Py), 7.92 (dd,
.sup.3J.sub.HH=9.0 Hz, .sup.4J.sub.FH=7.0 Hz, 3H, H-6), 6.53 (ddd,
.sup.3J.sub.HH=8.7 Hz, .sup.3J.sub.FH=8.7 Hz, .sup.4J.sub.HH=2.7
Hz, 3H, H-5), 5.92 (dd, .sup.3J.sub.FH=11.4 Hz, .sup.4J.sub.HH=2.7
Hz, 3H, H-3).
[0149] .sup.19F{.sup.1H} NMR (DMSO-d6): .delta. [ppm]=-178.4 (s,
1F), -109.5 (s, 3F).
[0150] T.sub.g: 197.degree. C.
Comparative Experiments on Hydrolysis Stability
Example 16
[0151] In a comparative experiment, the hydrolysis stability of the
polypodal aluminum complex
mono[tris(6-(5-fluoro-2-oxyphenyl)-2-pyridyl)fluoromethanato]aluminum(III-
) (Al-PPL-2), according to Example 13, was compared with that of
the structurally analogous but not polypodal variant
tris[5-fluoro-2-oxyphenyl)-2-pyridylato]aluminum(III), which is
described in the application JP 09176629 A2 as an OLED material. To
this end, a 10 mmolar solution of both complexes in dry DMSO-d6 was
prepared under an inert gas atmosphere. This solution was
characterized with the aid of .sup.1H NMR and of .sup.19F NMR
spectroscopy. Subsequently, these solutions were admixed at room
temperature with the 1000 molar amount of water and, after standing
for 10 min, characterized again with the aid of .sup.1H NMR and of
.sup.19F NMR spectroscopy. In the case of the polypodal aluminum
complex
mono[tris(6-(5-fluoro-2-oxyphenyl)-2-pyridyl)fluoromethanato]aluminum(III-
) (Al-PPL-2) according to Example 13, no change whatsoever in the
NMR could be detected. In contrast, in the case of the
non-polypodal
tris(5-fluoro-2-oxyphenyl)-2-pyridylato)aluminum(III), full
decomposition of the complex was observed, recognizable by
appearance of the proton and fluorine signals of the noncoordinated
ligands. Even after heating the above-described hydrolysis mixture
to 180.degree. C. for five hours, no sign of decomposition of the
polypodal aluminum complex Al-PPL-2 according to Example 13 could
be detected. This comparative experiment demonstrates clearly the
excellent hydrolysis stability of the inventive polypodal
complexes.
Production and Characterization of Organic Electroluminescent
Devices which Comprise Inventive Compounds
[0152] The OLEDs are produced by a general process which was
optimized in the individual case to the particular circumstances
(for example layer thickness variation to optimize the efficiency
and the color). Inventive electroluminescent devices can be
prepared as described, for example, in DE 10330761.3 or else DE
10261545.4.
Example 17
Device Structure
[0153] The examples which follow show the results of various OLEDs,
both with phosphorescence emitters and fluorescence emitters, in
which inventive compounds were used in the first case as hole
blocking materials, and BCP and BAlq as comparative materials (see
Table 1). In the second case, an inventive compound was used as the
electron transport material and AlQ.sub.3 as the corresponding
comparative material (see Table 2). The basic structure, the
materials and layer thicknesses used (apart from the HBLs) were
identical for better comparability.
[0154] According to the abovementioned general process,
phosphorescent OLEDs with the following structure were
obtained:
TABLE-US-00001 PEDOT (HIL) 60 nm (spin coated from water; purchased
as Baytron P from H.C. Starck; poly(3,4-ethylenedioxy-
2,5-thiophene)) NaphDATA (HTL) 20 nm (applied by vapor deposition;
purchased from SynTec; 4,4',4''-tris(N-
1-naphthyl-N-phenylamino)triphenyl- amine) S-TAD (HTL) 20 nm
(applied by vapor deposition; prepared according to WO 99/12888;
2,2',7,7'-tetrakis(diphenylamino)spiro- bifluorene) (EML) materials
and layer thicknesses: see Table 1 or 2 (HBL) if present, materials
and layer thicknesses: see Table 1 (ETL) materials and layer
thicknesses: see Table 1 or 2 Ba--Al (cathode) 3 nm of Ba, 150 nm
of Al thereon.
[0155] These OLEDs which were yet to be optimized were
characterized in a standard manner; for this purpose, the
electroluminescence spectra, the efficiency (measured in cd/A), the
power efficiency (measured in lm/W) were determined as a function
of the brightness and the lifetime. The lifetime is defined as the
time after which the starting brightness of the OLED has fallen by
half at a constant current density of 10 mA/cm.sup.2.
[0156] Table 1 compiles the results of the inventive OLEDs with use
of the phosphorescence emitter Ir(PPY).sub.3 doped to an extent of
10% in CBP (4,4'-bis(carbazol-9-yl)biphenyl) and use of the complex
Al-PPL2 according to Example 13 as a hole blocking material, and a
comparative example (with BAlq). Table 1 shows merely the hole
blocking layer and the electron transport layer (composition and
layer thickness). The electron transport material used was
AlQ.sub.3 (tris(8-hydroxyquinolinato)aluminum(III)), purchased from
SynTec. The other layers correspond to the abovementioned
structure.
[0157] Table 2 compiles the results of the inventive OLEDs with use
of a fluorescence emitter and use of the complex Al-PPL2 according
to Example 13 as the electron transport material, and some
comparative examples (with the electron transport material
AlQ.sub.3). Table 2 shows merely the emitter layer and the electron
transport layer (composition and layer thickness). The other layers
correspond to the abovementioned structure.
[0158] The abbreviations used above and in Tables 1 and 2
correspond to the following compounds:
##STR00061## ##STR00062##
TABLE-US-00002 TABLE 1 Max. Power efficiency efficiency Voltage (V)
(lm/W) at max. Lifetime (h) Example HBL ETL (cd/A) at 100
cd/m.sup.2 efficiency CIE (x, y) at 10 mA/cm.sub.2 Example T1
Al-PPL2 AlQ.sub.3 30.0 5.1 16.5 0.32/0.62 600 (10 nm) (20 nm)
Example T2 BAlq AlQ.sub.3 18.3 5.1 8.5 0.32/0.62 250 (comparison)
(10 nm) (20 nm) Example T3 Al-PPL2 -- 22.9 3.2 23.2 0.32/0.62 290
(20 nm) Example T4 BAlq -- 16.5 5.3 8.8 0.32/0.62 180 (comparison)
(20 nm)
TABLE-US-00003 TABLE 2 Max. Power efficiency efficiency Voltage (V)
(lm/W) at max. Lifetime (h) Example EML ETL (cd/A) at 100
cd/m.sup.2 efficiency CIE (x, y) at 10 mA/cm.sub.2 Example S1
S-DPVBi Al-PPL2 4.7 3.6 3.8 0.16/0.20 800 (30 nm) (10 nm) Example
S2 S-DPVBi Al-Q.sub.3 3.9 4.9 2.4 0.16/0.20 640 (comparison) (30
nm) (10 nm)
[0159] Table 1 shows that the use of Al-PPL2 in phosphorescent
OLEDs as the hole blocking material distinctly increases the
efficiency, in particular the power efficiency, of the OLEDs in
comparison to BAlq, and typically a doubling of the power
efficiency was observed. At the same time, the lifetime was also
distinctly improved. The examples show that even the electron
transport layer can be left out, which constitutes a distinct
simplification of the device structure.
[0160] In the case of the use of Al-PPL2 as the electron transport
material in fluorescent OLEDs, the efficiency, power efficiency and
lifetime are likewise distinctly improved, as can be taken from
Table 2.
[0161] In summary, it can be stated that phosphorescent and
fluorescent OLEDs which comprise inventive compounds such as
Al-PPL2 as hole blocking materials or electron transport materials
have high efficiencies with simultaneously long lifetimes and low
operating voltages, as can be taken readily from the examples
listed in Tables 1 and 2.
* * * * *