Metal complexes with bipodal ligands

• US 20070082284A1
• Filed: 10/21/2004
• Published: 04/12/2007
• Est. Priority Date: 10/30/2003
• Status: Active Grant

• Current Assignee: UDC Ireland Limited (Universal Display Corporation)
• Original Assignee: Merck Patent GmbH (Merck & Co., Inc.)
• Inventors: Stoessel, Philipp, Gerhard, Anja
• Granted Patent: US 9,029,539 B2
• Time in Patent Office: Days
• US Class Current: 430/84
• CPC Class Codes: C07D 213/26 Radicals substituted by halogen atoms or nitro radicals
• CPC Class Codes: C07D 213/30 Oxygen atoms
• CPC Class Codes: C07F 15/0033 Iridium compounds
• CPC Class Codes: C07F 15/0086 Platinum compounds
• CPC Class Codes: C07F 9/58 Pyridine rings
• CPC Class Codes: H10K 85/30 Coordination compounds
• CPC Class Codes: H10K 85/331 Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
• CPC Class Codes: H10K 85/342 comprising iridium
• CPC Class Codes: H10K 85/346 comprising platinum
• CPC Class Codes: H10K 85/361 Polynuclear complexes, i.e. complexes comprising two or more metal centers
• CPC Class Codes: Y02E 10/549 Organic PV cells

Abstract

The present invention describes novel metal complexes with bipolar ligands. Compounds of this type can be employed as functional materials in a number of different applications which can be ascribed to the electronics industry in the broadest sense.

Claims

1. Compounds of structure 1

characterised in that they contain a metal Met, coordinated to a tetradentate chelating ligand Lig of structure 2

where V is a bridging unit, characterised in that it contains 1 to 40 atoms from the third, fourth, fifth and/or sixth main group and connects the two ligand moieties L1 and L2, which may be identical or different on each occurrence, covalently to one another, and where the two ligand moieties L1 and L2 satisfy structure 3

where Cy1 and Cy2, identically or differently on each occurrence, correspond to a substituted or unsubstituted, saturated, unsaturated or aromatic homo- or heterocyclic ring, which is in each case bonded ionically, covalently or coordinatively to the metal via a ring atom or via an atom bonded exocyclically to the homo- or heterocyclic ring;

and where L3, identically or differently on each occurrence, is a mono- or bidentate, neutral or monoanionic ligand, and where a is 0, 1 or 2.

2. Compounds according to claim 1, characterised in that they are electrically neutral.

3. Compounds according to claim 1, characterised in that L1=L2.

4. Compounds according to claim 1, characterised in that the bridging unit V contains 1 to 6 atoms or is a 3- to 6-membered homo- or heterocyclic ring.

5. Compounds according to claim 1, characterised in that the following applies to the linking unit V:

V is BR¹, —

(CR₂)R¹B(CR₂)—

, —

O—

R¹B—

O—

, —

O—

(R¹O)B—

O—

, —

CR₂O—

R¹B—

OCR₂—

, —

(CR₂CR₂)R¹B(CR₂CR₂)—

, C═

O, C═

NR¹, C═

S, CR₂, CR(OH), CR(OR¹), C(NR¹)₂, —

(CR₂)R₂C(CR₂)—

, —

(CR₂CR₂)R₂C(CR₂CR₂)—

, —

(SiR₂)R₂C(SiR₂)—

, —

(SiR₂CR₂)R₂C(CR₂SiR₂)—

, —

(CR₂SiR₂)R₂C(SiR₂CR₂)—

, —

(SiR₂SiR₂)R₂C(SiR₂SiR₂)—

, cis-RC═

CR, 1,2-C₆H₄, 1,3-C₆H₄, SiR₂, Si(OH)₂, Si(OR¹)₂, —

(CR₂)R₂Si(CR₂)—

, —

(CR₂CR₂)R₂Si(CR₂CR₂)—

, —

(SiR₂)R₂Si(SiR₂)—

, —

(SiR₂CR₂)R₂Si(CR₂SiR₂)—

, —

(CR₂SiR₂)R₂Si(SiR₂CR₂)—

, —

(SiR₂SiR₂)R₂Si(SiR₂SiR₂)—

, R¹N, —

(CR₂)R¹N(CR₂)—

, —

(CR₂CR₂)R¹N(CR₂CR₂)—

, FP, FPO, R¹P, R¹As, R¹Sb, R¹Bi, R¹PO, R¹AsO, R¹SbO, R¹BiO, R¹PSe, R¹AsSe, R¹SbSe, R¹BiSe, R¹PTe, R¹AsTe, R¹SbTe, R¹BiTe, —

O—

R¹PO—

O—

, —

O—

(R¹O)PO—

O—

, —

CR₂O—

R¹PO—

OCR₂—

, —

OCR₂—

R¹PO—

CR₂O—

, O, S, Se, —

(CR₂)O(CR₂)—

, —

(CR₂)S(CR₂)—

, —

(CR₂)(O)S(CR₂)—

or —

(CR₂)(O)₂S(CR₂)—

or corresponding asymmetrical analogues;

R is, identically or differently on each occurrence, H, F, Cl, Br, I, NO₂, CN, a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, where one or more non-adjacent CH₂ groups may be replaced by —

R¹C═

CR¹—

, —

C≡

C—

, Si(R¹)₂, Ge(R¹)₂, Sn(R¹)₂, C═

O, C═

S, C═

Se, C═

NR¹, —

O—

, —

S—

, —

NR¹—

or —

CONR¹— and

where one or more H atoms may be replaced by F, or an aryl, aryloxy or heteroaryl group having 1 to 14 C atoms, which may be substituted by one or more non-aromatic radicals R, where a plurality of substituents R may in turn define a further mono- or polycyclic, aliphatic or aromatic ring system; and

R¹, R² are, identically or differently on each occurrence, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms.

6. Metal complexes according to claim 5, selected from compounds (1) to (8), each of which may also carry one or two additional ligands L3

where R, R¹ and R² have the same meaning as described in claim 5, and the other symbols and indices have the following meaning:

M is Be, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Sc, Y, La, Cr, Mo, W, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd or Hg;

L is, identically or differently on each occurrence, C, N or P;

Q is, identically or differently on each occurrence, N, O, S, Se or Te;

T is, identically or differently on each occurrence, N or P;

X is, identically or differently on each occurrence, CR, N or P;

Y is, identically or differently on each occurrence, NR¹, O, S, Se, Te, SO, SeO, TeO, SO₂, SeO₂ or TeO₂;

Z has the same meaning as described for V in claim 5;

c is, identically or differently on each occurrence, 0 or 1.

7. Metal complexes according to claim 5, selected from compounds (9) to (12), each of which may also carry one or two additional ligands L3

where the symbols and indices R, R¹ and R² have the same meanings as in claim 5 and

M is Be, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Sc, Y, La, Cr, Mo, W, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd or Hg;

L is, identically or differently on each occurrence, C, N or P;

Q is, identically or differently on each occurrence, N, O, S, Se or Te;

T is, identically or differently on each occurrence, N or P;

X is, identically or differently on each occurrence, CR, N or P;

Y is, identically or differently on each occurrence, NR¹, O, S, Se, Te, SO, SeO, TeO, SO₂, SeO₂ or TeO₂;

Z has the same meaning as described for V in claim 5;

c is, identically or differently on each occurrence, 0 or 1.

8. Metal complexes according to claim 5, selected from compounds (13) to (30), each of which may also carry one or two additional ligands L3

where the symbols and indices R, R¹ and R² have the same meanings as in claim 5 and

M is Be, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Sc, Y, La, Cr, Mo, W, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd or Hg;

L is, identically or differently on each occurrence, C, N or P;

Q is, identically or differently on each occurrence, N, O, S, Se or Te;

T is, identically or differently on each occurrence, N or P;

X is, identically or differently on each occurrence, CR, N or P;

Y is, identically or differently on each occurrence, NR¹, O, S, Se, Te, SO, SeO, TeO, SO₂, SeO₂ or TeO₂;

Z has the same meaning as described for V in claim 5;

c is, identically or differently on each occurrence, 0 or 1.

9. Metal complexes according to claim 1, characterised in that ligand L3, if present, is a bidentate chelating ligand.

10. Metal complexes according to claim 9, characterised in that L3 is a monoanionic ligand which is identical to or different from ligand moieties L1 and L2 or in that L3 is a ligand of structure (4)

where R³, identically or differently on each occurrence, represents H, a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ alkoxy group, a C₄ to C₂₀ aryl or heteroaryl group or a C₄ to C₂₀ aryloxy or heteroaryloxy group, and one or more H atoms may be replaced by F.

11. Compounds according to claim 6, characterised in that the symbol M=Be, Mg, Pt or Zn, and the index a=0.

12. Compounds according to claim 11, characterised in that the symbol c=0 and M=Pt.

13. Compounds according to claim 6, characterised in that the symbol M=Rh or Ir, and the index a=1 in the case of a bidentate monoanionic ligand L3 or a=2 in the case of a monodentate monoanionic ligand L3.

14. Compounds according to claim 6, characterised in that the symbol L=C or N.

15. Compounds according to claim 1, characterised in that the symbol Q=O or S.

16. Compounds according to claim 6, characterised in that the symbol T=N.

17. Compounds according to claim 6, characterised in that the symbol X═

CR or N.

18. Compounds according to claim 6, characterised in that the symbol Z=BR¹, CR₂, CO, SiR¹₂, R¹N, FP, FPO, R¹P, R¹PO, —

CR₂CR₂—

, —

CR₂—

O—

CR₂—

, —

O—

(OR¹)PO—

O—

, cis-CR═

CR, —

CR₂—

BR¹—

CR₂—

, —

CR₂—

CO—

CR₂—

, —

CR₂—

CR₂—

CR₂—

or —

CR₂—

NR¹—

CR₂.

19. Compounds according to claim 5, characterised in that the symbol R═

H, F, Cl, Br, I, CN, a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 6 C atoms or an aryl or heteroaryl group having 3 to 10 C atoms, which may be substituted by one or more non-aromatic radicals R, where a plurality of substituents R, both on the same ring and also on the two different rings, may together in turn define a further mono- or polycyclic ring system.

20. Compounds (31) to (60)

where the symbols and indices L, Q, T, X, Y, Z, R, R¹, R² and c have the same meanings as in claim 7, apart from the compounds bis(6-phenyl-2-pyridyl)methane, bis(6-phenyl-2-pyridyl) ketone, bis(6-(1-hydroxy-3,5-di-tert-butyl)phenyl-2-pyridyl)methanol, 2,2′

-thiobis(3-cyano-2,4-diphenyl)pyridine, bis(6-(3-phenyl)phenyl-2-pyridyl)methane and isomers.

21. A process for the preparation of the compounds of structure 1

characterised in that they contain a metal Met, coordinated to a tetradentate chelating ligand Lig of structure 2

where V is a bridging unit, characterised in that it contains 1 to 40 atoms from the third, fourth, fifth and/or sixth main group and connects the two ligand moieties L1 and L2, which may be identical or different on each occurrence, covalently to one another, and where the two ligand moieties L1 and L2 satisfy structure 3

where Cy1 and Cy2, identically or differently on each occurrence, correspond to a substituted or unsubstituted, saturated, unsaturated or aromatic homo- or heterocyclic ring, which is in each case bonded ionically, covalently or coordinatively to the metal via a ring atom or via an atom bonded exocyclically to the homo- or heterocyclic ring;

and where L3, identically or differently on each occurrence, is a mono- or bidentate, neutral or monoanionic ligand, and where a is 0, 1 or 2.

which comprises reacting compounds (31) to (60) according to claim 20 with metal alkoxides of compound (61), with metal ketoketonates of compound (62), metal halides, carboxylates, nitrates and sulfates of compound (63) or alkyl- or arylmetal compounds of compound (64)

I.

where the symbols M and R¹,

M is Be, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Sc, Y, La, Cr, Mo, W, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd or Hg;

R¹ are, identically or differently on each occurrence, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms;

and the symbol A=F, Cl, Br, I, OH, formate, acetate, propionate, benzoate, nitrate or sulfate, and L′

is a monodentate ligand and n=1, 2 or 3 and q=0, 1, 2 or 3.

22. Compounds according to claim 1, characterised in that their purity (determined by ¹H-NMR and/or HPLC) is greater than 99%.

23. Conjugated, partially conjugated and/or non-conjugated polymers or dendrimers containing one or more compounds of structure 1

characterised in that they contain a metal Met, coordinated to a tetradentate chelating ligand Lig of structure 2

where V is a bridging unit, characterised in that it contains 1 to 40 atoms from the third, fourth, fifth and/or sixth main group and connects the two ligand moieties L1 and L2, which may be identical or different on each occurrence, covalently to one another, and where the two ligand moieties L1 and L2 satisfy structure 3

where Cy1 and Cy2, identically or differently on each occurrence, correspond to a substituted or unsubstituted, saturated, unsaturated or aromatic homo- or heterocyclic ring, which is in each case bonded ionically, covalently or coordinatively to the metal via a ring atom or via an atom bonded exocyclically to the homo- or heterocyclic ring;

and where L3, identically or differently on each occurrence, is a mono- or bidentate, neutral or monoanionic ligand, and where a is 0, 1 or 2,

or compounds (1) to (12)

wherein

R is, identically or differently on each occurrence, H, F, Cl, Br, I, NO₂, CN, a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, where one or more non-adjacent CH₂ groups may be replaced by —

R¹C═

CR¹—

, —

C≡

C—

, Si(R¹)₂, Ge(R¹)₂, Sn(R¹)₂, C═

O, C═

S, C═

Se, C═

NR¹, —

O—

, —

S—

, —

NR¹—

or —

CONR¹— and

where one or more H atoms may be replaced by F, or an aryl, aryloxy or heteroaryl group having 1 to 14 C atoms, which may be substituted by one or more non-aromatic radicals R, where a plurality of substituents R may in turn define a further mono- or polycyclic, aliphatic or aromatic ring system;

R¹, R² are, identically or differently on each occurrence, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms;

M is Be, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Sc, Y, La, Cr, Mo, W, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd or Hg;

L is, identically or differently on each occurrence, C, N or P;

Q is, identically or differently on each occurrence, N, O, S, Se or Te;

T is, identically or differently on each occurrence, N or P;

X is, identically or differently on each occurrence, CR, N or P;

Y is, identically or differently on each occurrence, NR¹, O, S, Se, Te, SO, SeO, TeO, SO₂, SeO₂ or TeO₂;

Z has the same meaning as described for V in claim 5;

and

c is, identically or differently on each occurrence, 0 or 1;

or compounds (13) to (30) according to claim 8.

24. Polymers or dendrimers according to claim 23, characterised in that at least one radical R represents a bond to the polymer or dendrimer.

25. Polymers according to claim 24, characterised in that the polymer is selected from the group of the polyfluorenes, polyspirobifluorenes, poly-para-phenylenes, polydihydrophenanthrenes, polyindenofluorenes, polycarbazoles, polythiophenes, polyketones, polyvinylcarbazoles or from copolymers which have a plurality of the units mentioned here.

26. An electronic device comprising at least a polymer, a copolymer or a dendrimer according to claim 23.

27. Electronic device according to claim 26, characterised in that it is an organic light-emitting diode (OLED), an organic integrated circuit (O-IC), an organic field-effect transistor (OFET), an organic thin-film transistor (OTFT), an organic solar cell (O-SC) or an organic laser diode (O-laser).

28. An electronic device comprising at least one compound according to claim 1.