WO2004043974A1 - Production de complexes d'iridium - Google Patents

Production de complexes d'iridium Download PDF

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Publication number
WO2004043974A1
WO2004043974A1 PCT/JP2003/014192 JP0314192W WO2004043974A1 WO 2004043974 A1 WO2004043974 A1 WO 2004043974A1 JP 0314192 W JP0314192 W JP 0314192W WO 2004043974 A1 WO2004043974 A1 WO 2004043974A1
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formula
group
ring
aryl group
iridium
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PCT/JP2003/014192
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English (en)
Inventor
Yuji Nakayama
Yoshimasa Matsushima
Yoji Hori
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Takasago International Corporation
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0033—Iridium compounds

Definitions

  • the present invention relates to a process for producing a trivalent hexadentate ortho- etallated iridium complex being useful as a material for a light-emitting device and the like.
  • Organic electroluminescence (EL) devices have received attention in view of the practical use as display devices of the next generation including an ultra-slimline display or electronic paper since they can emit light of high luminance at a lower voltage.
  • the organic EL device is an emission device utilizing electroluminescence (EL) based on the same principle as in LED and characterized by using an organic fluorescent substance as an emission material.
  • EL electroluminescence
  • a variety of emission materials for organic EL devices have been developed, and particularly trivalent hexadentate ortho-metallated iridium complexes such as bis (2-phenylpyridinato-N,C 2 ') iridium acetylacetonate (re- ferred to as Compound 3-1 below) and tris (2-phenylpyridinato-N, C 2 ' ) iridium (referredto as Compound 5-1 below) have received attention since they emit phosphorescence from a triplet excitation state with a characteristic higher quantum efficiency than the fluorescent emission and its wavelength of emission can optionally be adjusted by changing the chemical structure of the ligand.
  • trivalent hexadentate ortho-metallated iridium complexes such as bis (2-phenylpyridinato-N,C 2 ') iridium acetylacetonate (re- ferred to as Compound 3-1 below) and tris (2-phenylpyridinato-N, C 2
  • a light-emitting device using Compound 5-1 as discussed below has a value as high as 9% in an external quantum efficiency for green-light emission (see Non-patent document 1).
  • Bis [2- (2' -benzothienyl) pyridinato-N, C 3 ' ) iridium (III) acetylacetonate (referred to as Compound 3-7 below) has been reported to be a red phosphorescence-emitting material with very high quantum efficiency and color purity (see Non-patent document 2) . From the above fact, research on the design for peripheral devices as well as an efficient method for synthesis of the complexes have now actively be conducted aiming at actual use of them.
  • the reported yield at the 1st step is 75% or higher, 75-90% at the 2nd step, and 85% at the 3rd step (see Non-patent document 5) .
  • the complexes containing the different ligands are 75% or higher, 75-90% at the 2nd step, and 85% at the 3rd step (see Non-patent document 5) .
  • Patent document 1 WO 02/02714
  • Patent document 2 WO 02/15645
  • Patent document 3 JP-A No.105055
  • Non-patent document 1 Baldo M.A. et al . , Appl. Phys . Lett.,
  • Non-patent document 2 Adachi, C. et al . , Appl. Phys. Lett.,
  • Non-patent document 3 M. Nonoyama, Bull. Chem. Soc. Jpn.,
  • Non-patent document 4 S. Lamansky, et al . , J. Am. Chem. Soc,
  • Non-patent document 5 S. Lamansky, et al . , Inorg. Chem.,
  • Trivalent hexadentate ortho-metallated iridium complexes have been expected as light-emitting materials for organic electroluminescence (EL) devices.
  • the production method thereof has to pass through complicated steps, and accordingly it has been desired that a more convenient process for producing such complexes in high yield will be established toward the practical use of the complexes as the light-emitting material.
  • An object of the present invention is to provide a convenient and efficient process for producing a trivalent hexadentate ortho-metallated iridium complex being useful as a material for a light-emitting device.
  • Thepresent inventors have conducted research assiduously to develop an efficient and convenient process for producing a trivalent hexadentate ortho-metallated iridium dinuclear complex in a milder condition. As a result, they have found that the reaction using a monovalent iridium dinuclear complex represented by the formula (I) as a starting material gives a trivalent hexadentate ortho-metallated iridium dinuclear complex represented by the formula (II) in a milder condition efficiently in quantitative yield within a short period of time .
  • the complex of the formula (II) produced in this process can be applied to the synthesis of other complexes.
  • the present inventors further conducted research assiduously to establish a commercially applicable process for producing iridium complexes, and as a result they have found that the trivalent hexadentate ortho-metallated iridium dinuclear complex of the formula (II) produced in this reaction can be applied without isolation and purification from the reaction mixture to the reaction with a compound of the formula (VII) or (VIII) and a base or a compound of the formula (VI) and a silver salt placed in the same reaction vessel to give the complex in which the ligands are the same with each other (the formula (V) ) as the complex (the formula e (III) and (IV)), in which the ligands are different, in a conventional way in high yield, wherein the individual products can optionally be produced separately.
  • the invention has been completed based on the finding mentioned above.
  • the invention provides a process for producing a trivalent hexadentate ortho-metallated iridium complex with an iridium compound and a coordination compound as starting materials, which is characterized in that a monovalent iridium dinuclear complex represented by the following formula (I) is used as the raw iridium compound:
  • the invention provides a process for producing a trivalent hexadentate ortho-metallated iridium dinuclear complex represented by the formula (II) :
  • ring B represents an optionally substituted aryl group or heteroaryl group
  • the ring C represents an optionally substituted nitrogen-containing aryl group
  • the rings B and C may be taken with each other to form a fused ring
  • X has the same meanings as mentioned above
  • the invention also provides a process for converting the complex of the formula (II) produced in the above process into a trivalent hexadentate ortho-metallated iridium complex representedby the formula (III), (IV) or (V) .
  • the complex of the formula (II) without isolating and purifying from the reaction mixture can be used as an intact reaction mixture in the next step. This is another major characteristic in the invention.
  • the invention provides a process for producing a trivalent hexadentate ortho-metallated iridium complex represented by the formula (III) :
  • R 1 and R 3 each represent independently an alkyl group, alkoxy group, aryl group or heteroaryl group;
  • R 2 represents a hydrogen atom, alkyl group, aryl group or heteroaryl group;
  • R 1 and R 2 or R 2 and R 3 may be taken together with the adjacent carbon atom to form a ring; the rings B and C, each has the same meanings as mentioned above) characterized in that reacting a monovalent iridium dinuclear complex of the formula (I) with a compound of the formula (VI) to give a compound of the formula (II), followed by reacting the compound of the formula (II) with a compound of the formula
  • the invention also provides a process for producing a trivalent hexadentate ortho-metallated iridium complex represented by the formula (IV) :
  • rings B andC eachhave the same meanings as mentioned above, and the ring D represents an optionally substituted pyridyl group.
  • the rings B and C may be taken with each other to form a fused ring
  • reacting a monovalent iridium dinuclear complex of the formula (I) with a compound of the formula (VI) followed by the reaction with a compound of the formula (VIII) :
  • the invention also provides a process for producing a trivalent hexadentate ortho-metallated iridium complex represented by the formula (V) :
  • This process of the invention may be carried out step by step or successively.
  • the reaction may be conducted in the same reaction vessel, i.e., one-pot reaction, by adding a silver salt into the reaction mixture of the 1st step.
  • the processes for producing trivalent hexadentate ortho-metallated iridium complexes of the present invention are characterized by using a monovalent iridium dinuclear complex represented by the formula (I) as the raw material.
  • the processes of the present invention are also characterized in that the objective trivalent hexadentate ortho-metallated iridium complexes can be produced in the same reaction vessel, i.e., one-pot reaction, using the monovalent iridium dinuclear complex represented by the formula (I) as the raw material.
  • iridium complexes containing a variety of coordination compounds as ligands such as trivalent hexadentate ortho-metallated iridium complexes represented by the following formula (II)
  • ring B represents an optionally substituted aryl group or heteroaryl group
  • the ring C represents an optionally substituted nitrogen-containing aryl group
  • the ring D represents an optionally substituted pyridyl group
  • the rings B and C may be taken with each other to form a fused ring
  • X represents a halogen atom
  • R 1 and R 3 each represents independently an alkyl group, alkoxy group, aryl group or heteroaryl group
  • R 2 represents a hydrogen atom, alkyl group, aryl group or heteroaryl group
  • R 1 and R 2 or R 2 and R 3 may be taken together with the adjacent carbon atom to form a ring
  • a non-conjugated diene compound represented by A in the formula (I) may be cyclic or acyclic ones and may have a substituent or substituents as long as they have no adverse effect.
  • the cyclic diene compound includes any one of monocyclic, polycyclic, condensed cyclic, and cross-linked cyclic.
  • the preferred non-conjugated diene compound represented by A includes, for example, of those having 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms, with a cyclic non-conjugated diene compound being particularly preferred.
  • Specific examples of the preferred non-conjugated diene compounds include cyclic compounds such as 1, 5-cyclooctadiene (cod), and bicyclo [2.2. l]hepta-2, 5-diene (nbd) .
  • Ahalogen atomrepresentedbyX inthe formula (I) includes, for example, fluorine atom, chlorine atom, bromine atom, and iodine atom, with chlorine atom being preferred.
  • the preferredmonovalent iridium dinuclear complexes of the formula (I) may be represented by the following formula (IX) or(X) :
  • the optionally substituted aryl group or heteroaryl group represented by the ring B includes aryl groups, substituted aryl groups, heteroaryl groups and substituted heteroaryl groups.
  • An aryl group is exemplified by a monocyclic, polycyclic or condensed cyclic aryl group having 6 to 14 carbon atoms. Concrete examples of the aryl group include phenyl, naphthyl, anthryl, and the like.
  • a heteroaryl group is exemplified by a five- or six-membered monocyclic, polycyclic or condensed cyclic aromatic heterocyclic group containing, for example, 1 to 3 nitrogen atoms, oxygen atoms and/or sulfur atoms as heteroatoms .
  • Concrete examples of the heteroaryl group include pyridyl, imidazolyl, thiazolyl, furyl, benzofuryl, thienyl, benzothienyl, and the like.
  • a substituted aryl group includes the aryl group as mentioned above in which at least one of the hydrogen atoms is substitutedbya substituent .
  • Asubstitutedheteroaryl group includes the heteroaryl group as mentioned above in which at least one of the hydrogen atoms is substituted by a substituent .
  • the substituents in these groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, alkoxy groups, alkylthio groups, a cyano group, acyl groups, alkyloxycarbonyl groups, a nitro group, halogen atoms, alkylenedioxy groups, and the like.
  • the alkyl group may be a straight or branched chain or cyclic group having, for example, 1 to 15 carbon atoms, preferably 1 to 6 carbon atoms.
  • alkyl group examples include methyl, ethyl, n-propyl, 2-propyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, tert-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
  • the alkenyl group may be a straight or branched chain alkenyl group of for example 2 to 6 carbon atoms. Concrete examples of the alkenyl group include ethenyl, propenyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, and the like.
  • the alkynyl group may be a straight or branched chain alkynyl group having, for example, 2 to 5 carbon atoms. Concrete examples of the alkynyl group include ethynyl, 1-propynyl, 3-propynyl, 1-butynyl, 3-butynyl, pentynyl, and the like.
  • the aryl group maybe a straight orbranched chain aryl group having, for example, monocyclic, polycyclic or condensed cyclic aryl groups of 6 to 14 carbon atoms.
  • Concrete examples of the aryl group include phenyl, naphthyl, anthryl, and the like.
  • the heteroaryl group may be a straight or branched chain heteroaryl group having, for example, five- or six-membered monocyclic, polycyclic or condensed cyclic aromatic heterocyclic group containing 1 to 3 heteroatoms, e.g., nitrogen atom, oxygen atom, sulfur atom, etc., specifically, pyridyl, imidazolyl, thiazolyl, furyl, benzofuryl, thienyl, benzothienyl, and the like.
  • the alkoxy group maybe a straight or branched chain alkoxy group having, for example, 1 to 6 carbon atoms .
  • Concrete examples of the alkoxy group include methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, and the like.
  • the alkylthio group may be a straight or branched chain alkylthio group of, for example, 1 to 6 carbon atoms.
  • alkylthio group examples include methylthio, ethylthio, n-propylthio, 2-propylthio, n-butylthio, sec-butylthio, tert-butylthio, pentylthio, hexylthio, and the like.
  • the acyl group may be a straight or branched chain or cyclic acyl group, for example, the acyl group derived from a carboxylic acid of 1 to 7 carbon atoms.
  • Concrete examples of the acyl group include formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, benzoyl, and the like.
  • the alkyloxycarbonyl group includes straight or branched chain alkyloxycarbonyl groups of for example 2 to 7 carbon atoms. Concrete examples of the alkyloxycarbonyl groups include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, n-butyloxycarbonyl, tert-butyloxycarbonyl, pentyloxycar- bonyl, hexyloxycarbonyl, and the like.
  • the halogen atom includes, for example, fluorine atom, chlorine atom, bromine atom, and iodine atom.
  • the alkylenedioxy group includes those of for example 1 to 3 carbon atoms, specifically, for example, methylenedioxy, ethylenedioxy, propylenedioxy, and the like.
  • a nitrogen-containing aryl group in the ring C means the heteroaryl group containing at least one nitrogen atom as heteroatom in the ring, which may further contain 1 or 2 heteroatom (s) such as nitrogen atom, oxygen atom or sulfur atom, including five- or six-membered monocyclic, polycyclic or condensed cyclic aromatic heterocyclic group, wherein at least one of the nitrogen atoms is placed so as to coordinate with the iridiumatom.
  • the nitrogen-containing aryl group includes, for example, pyridyl, quinolyl, and the like.
  • the nitrogen-containing aryl group in the ring C may be substituted, and the substituted nitrogen-containing aryl group includes those as mentioned above in which at least one hydrogen atom may be substituted by a substituent.
  • the substituent may be the same as that exemplified in the substituted aryl and heteroaryl groups in the ring B.
  • the ring which is formed by combination of the ring B and the ring C includes fused rings such as benzoquinoline .
  • the preferred example of the trivalent hexadentate ortho-metallated iridium complexs of the formula (II) produced by the process of the present invention includes those represented by the following formula (XI) :
  • R 8 , R 9 , R 10 , and R 11 each represents independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthio group, a cyano group, acyl group, alkyloxycarbonyl group, a nitro group, or halogen atom;
  • X represents a halogen atom;
  • the ring B has the same meanings as mentioned above; the ring B may be taken with the pyridyl group binding to the ring B to form a ring
  • the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthio group, acyl group, and alkyloxycarbonyl group represented by R 8 , R 9 , R 10 , and R 11 in the formula (XI) may have an additional substituent or substituents, which may be exemplified by those mentioned in the substituted aryl or heteroaryl groups in the formula (II) .
  • the halogen atom represented by X in the formula (XI) is also as mentioned above.
  • the preferred ring B includes phenyl group, substituted phenyl group, naphthyl group, substitutednaphthyl group, furyl group, substituted furyl group, benzofuryl group, substituted benzofuryl group, thienyl group, substituted thienyl group, benzothienyl group, substituted benzothienyl group, and the like.
  • the substituent on the substituted phenyl group, substituted naphthyl group, substituted furyl group, substituted benzofuryl group, substituted thienyl group, and substituted benzothienyl group may be exemplified by those mentioned in the substituted aryl group or heteroaryl group in the formula (II) .
  • trivalent hexadentate ortho-metallated iridium complexs representedby the formula (II) include the following compounds (Il-i) to (II-xvi) .
  • the respective groups i.e., the ring B, the ring C, alkyl group, alkoxy group, aryl group, and heteroaryl group, are the same as described in the formula
  • Such groups may further be substituted by a substituent or substituents including those as mentioned'in the substituted aryl or heteroaryl groups in the formula (II) as mentioned above .
  • the preferred substituent includes halogen atoms such as fluorine atom, chlorine atom andbromine atom, which exemplifies substituents such as haloalkyl group, haloalkoxy group, haloaryl group, and halogenated heteroaryl group.
  • (III) may be a straight or branched chain or cyclic group, for example, alkyl group having 1 to 6 carbon atoms.
  • alkyl group examples include methyl, ethyl, n-propyl, 2-propyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, tert-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
  • halogenated alkyl group includes, for example, the above-mentioned alkyl groups having 1 to 6 carbon atoms halogenated by one or two or more halogen atom(s) (e.g., fluorinated, chlorinated, brominated, or iodinated) .
  • halogen atom(s) e.g., fluorinated, chlorinated, brominated, or iodinated
  • Concrete examples of the halogenated alkyl group include chloromethyl, bromomethyl, trifluoromethyl, 2-chloroethyl, 3-chloropropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl, and the like.
  • An aryl group includes, for example, the aryl group having of 6 to 14 carbon atoms.
  • aryl group examples include phenyl, naphthyl, anthryl, and the like.
  • a heteroaryl group is exemplified by a five- or six-membered monocyclic or polycyclic aromatic heterocyclic group containing, for example, 1 to 3 nitrogen atoms, oxygen atoms and/or sulfur atoms as heteroatoms.
  • the heteroaryl group examples include pyridyl, imidazolyl, thiazolyl, furyl, benzofuryl, thienyl, benzothienyl, and the like .
  • a ring may be a monocycle or polycycle, with a five- or six-membered ring being preferred.
  • Specific examples of the formed rings are cyclopentane, cyclohexane, and the like.
  • the preferred example of the trivalent hexadentate ortho-metallated iridium complexs represented by the formula (III) includes those representedby the following formula (XII)
  • the preferred ring B includes phenyl group, substituted phenyl group, naphthyl group, substitutednaphthyl group, furyl group, substituted furyl group, benzofuryl group, substituted benzofuryl group, thienyl group, substituted thienyl group, benzothienyl group, substituted benzothienyl group, and the like.
  • the substituent on the substituted phenyl group, substituted naphthyl group, substituted furyl group, substituted benzofuryl group, substituted thienyl group, and substituted benzothienyl group may be exemplified by those mentioned in the substituted aryl group or heteroaryl group in the formula (II) .
  • (III) include the following compounds (Ill-i) to (III-xvi) .
  • the rings B and C each has the same meanings as mentioned above; the ring D represents an optionally substituted pyridyl group; and the rings B and C may be taken with each other to form a fused ring) produced by the process of the present invention, the rings B and C each has the same meanings as in the formula (II) .
  • the ring D contains a pyridine ring, which may be a monocyclic, polycyclic or condensed cyclic ring, in which one or two or more of the hydrogen atom ( s) may be substituted by a substituent or substituents.
  • R 4 , R 5 , R 6 , and R 7 each represents independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthio group, a cyano group, acyl group, alkyloxycarbonyl group, a nitro group, or halogen atom;
  • R 8 , R 9 , R 10 , R 1:L ,and the ring B each has the same meanings as mentioned above
  • alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthio group, acyl group, and alkyloxycarbonyl group represented by R 8 , R 9 , R 10 , R 11 , R 4 , R 5 , R 6 , and R 7 in the formula (XIII) may be the same as mentioned above.
  • These groups may have an additional substituent or substituents, which may be the same as those mentioned in the substituted aryl or heteroaryl groups in the formula (II) .
  • the preferred ring B includes phenyl group, substituted phenyl group, naphthyl group, substitutednaphthyl group, furyl group, substituted furyl group, benzofuryl group, substituted benzofuryl group, thienyl group, substituted thienyl group, benzothienyl group, substituted benzothienyl group, and the like.
  • the substituent on the substituted phenyl group, substituted naphthyl group, substituted furyl group, substituted benzofuryl group, substituted thienyl group, and substituted benzothienyl group may be exemplified by those mentioned in the substituted aryl group or heteroaryl group in the formula (II) .
  • trivalent hexadentate ortho-metallated iridium complexes represented by the formula (IV) are the following compounds (IV-i) to (IV-viii).
  • the preferred trivalent hexadentate ortho-metallated iridium complexes of the formula (V) include those represented by the following formula (XIV) :
  • R 8 , R 9 , R 10 , R 11 , and the ring B each has the same meanings as mentioned above; and the ring B may be taken with the pyridyl group binding to the ring B to form a ring).
  • the preferred ring B includes phenyl group, substituted phenyl group, naphthyl group, substituted naphthyl group, furyl group, substituted furyl group, benzofuryl group, substituted benzofuryl group, thienyl group, substituted thienyl group, benzothienyl group, substituted benzothienyl group, and the like.
  • the substituent on the substituted phenyl group, substituted naphthyl group, substituted furyl group, substituted benzofuryl group, substituted thienyl group, and substituted benzothienyl group may be exemplified by those mentioned in the substituted aryl group or heteroaryl group in the formula (II) .
  • trivalent hexadentate ortho-metallated iridium complexes represented by the formula (V) are the following compounds (V-i) to (V-x) .
  • the coordination compound in the manufacturing process of the present invention means the compound having a chemical structure capable of forming a ligand of iridium complex.
  • a coordination compound which can entirely become a ligand for an iridium complex, or fromwhich the partial atom or atomic group may leave to form a ligand for an iridium complex.
  • the rings B and C are the same as those described in the above-mentioned formula (II) .
  • the preferred examples of the compounds represented by the formula (VI) include the compounds represented by the following formula (XV) :
  • R 8 , R 9 , R , and R each represents independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthio group, a cyano group, acyl group, alkyloxycarbonyl group, a nitro group, or halogen atom;
  • the ring B represents an optionally substituted aryl or heteroaryl group; or the ring B may be taken with the pyridyl group binding to the ring B to form a ring
  • the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthio group, acyl group, and alkyloxycarbonyl group represented by R 8 , R 9 , R 10 , and R 11 in the formula (XV) may have an additional substituent or substituents, which may be exemplified by those mentioned in the substituted aryl or heteroaryl groups in the formula (II) .
  • the preferred ring B includes phenyl group, substituted phenyl group, naphthyl group, substituted naphthyl group, furyl group, substituted furyl group, benzofuryl group, substituted benzofuryl group, thienyl group, substituted thienyl group, benzothienyl group, substituted benzothienyl group, and the like.
  • the substitutent on the substitutedphenyl group, substituted naphthyl group, substituted furyl group, substituted benzofuryl group, substituted thienyl group, and substituted benzothienyl group may be exemplified by those mentioned in the substituted aryl group or heteroaryl group in the formula (II) .
  • Vl-xvi (Vl-xvii) (Vl-xviii) (Vl-xix) (VI-xx)
  • the alkyl group, alkoxy group, aryl group and heteroaryl group may have an additional susbstituent or substituents, which may be the same as those described in the formula (III).
  • the groups represented by R 1 , R 2 and R 3 in the compound represented by the formula (VII) are also the same as described in the formula (III) .
  • the compounds represented by the formula (VII) used in the invention are specifically exemplified by acetylacetone, 2-acetylcyclohexanone, 2-trifluoroacetylcyclopentanone, 1, 3-diphenyl-l, 3-propanedione, 2,2, 6, 6-tetramethyl-3, 5-heptanedione, 3-methyl-2, 4-pentanedione, 1, 1, 1, 5, 5, 5-hexafluoro-2, 4-pentanedione,
  • the ring D has the same meanings as mentioned above
  • the ring D has the same meanings as mentioned in the formula (IV) .
  • the preferred examples of the compounds represented by the formula (VIII) include pyridinecarboxylic acids or derivatives thereof represented by the following formula (XVI) :
  • R , R , R , and R each represents independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthio group, a cyano group, acyl group, alkyloxycarbonyl group, a nitro group, or halogen atom
  • R 4 , R 5 , R 6 , and R 7 in the formula (XVI) the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthio group, acyl group, and alkyloxycarbonyl group are the same as described above. These groups may have an additional substituent or substituents, which may be the same as mentioned in the substituted aryl and heteroaryl groups in the formula (II) .
  • Scheme 1 illustrated the reaction formula of aprocess for producing a trivalent hexadentate ortho-metallated iridium dinuclear complex of the formula (II) from a monovalent iridium dinuclear complex of the formula (I) as a starting compound.
  • the trivalent hexadentate ortho-metallated iridium dinuclear complex represented by the formula (II) may readily be produced by reacting a monovalent iridium dinuclear complex of the formula (I) with a compound of the formula (VI) in or without a suitable solvent if required under an atmosphere of inert gas.
  • (VI) may be used usually in the amount appropriately selected from the range of 2 to 50 equivalents, preferably 3 to 20 equivalents, morepreferably 4 to 6 equivalents to themonovalent iridium dinuclear complex of the compound represented by the formula (I) .
  • the process of the present invention is preferably carried out in the presence of the solvent.
  • a solvent for example, an amide such as N,N-dimethylformamide, formamide, or N,N-dimethylacetamide; a cyano-containing organic compound such as acetonitrile; a halogenated hydrocarbon such as dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, or o-dichlorobenzene; an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, or decane; an aromatic hydrocarbon such as benzene, toluene, or xylene; an ether such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, di- methoxyethane, tetrahydrofuran, 1,4-dioxane,
  • a solvent for example
  • solvents may be used alone or in combination of two or more members.
  • an alcohol such as methanol, ethanol, 2-propanol, n-butanol, tert-butanol, or 2-ethoxyethanol
  • a polyhydric alcohol such as ethylene glycol, propylene glycol, 1, 2-propanediol, or glycerin
  • water alone or in combination of two or more members.
  • the amount of the solvent to be used is not limited to the amount of 1 to 200 parts, preferably about 5 to 50 parts for 1 part of the monovalent iridium dinuclear complex represented by the formula (I).
  • the reaction is preferably carried out in an atmosphere of an inert gas.
  • an inert gas for example, nitrogen gas, argon gas, or the like can be used.
  • the reaction may also be carried out in combination with an ultrasonic generator.
  • the reaction temperature is selected usually from the range of 25°C to 300°C, preferably from 60°C to 200°C, and more preferably from 80°C to 150°C.
  • the reaction time is selected usually from the range of 10 minutes to 72 hours, preferably 30 minutes to 48 hours, more preferably 1 to 6 hours.
  • resulting product is preferably used in the succeeding reaction without any post-treatment, but if necessary it may be carried out, post-treatment isolation and purification.
  • the post-treatment maybe conducted, for example, by extraction with the reaction product, filtration of the precipitate, crystallization with addition of a solvent, evaporation of the solvent, and so on. These operations may be conducted alone or in combination.
  • the purification is achieved, for example, by column chromatography, recrys- tallization, sublimation, and so on, which may be conducted alone or in combination.
  • Scheme 2 illustrated the reaction formula of aprocess for producing a trivalent hexadentate ortho-metallated iridium complex represented by the formula (III) from a monovalent iridium dinuclear complex of the formula (I) as a starting compound.
  • the trivalent hexadentate ortho-metallated iridium dinuclear complex represented by the formula (II) may readily be produced by reacting a monovalent iridium dinuclear complex represented by the formula (I) with a compound represented by the formula (VI) in or without a suitable solvent if required under an atmosphere of inert gas.
  • the resulting trivalent hexadentate ortho-metallated iridium dinuclear complex represented by the formula (II) is allowed to react with a compound of the formula (VII ) inorwithout a suitable solvent if required in the presence of a base and if required under an atmosphere of inert gas to smoothly give the trivalent hexadentate ortho-metallated iridium dinuclear complex represented by the formula (III) .
  • the trivalent hexadentate ortho-metallated iridiumdinuclear complex representedby the formula (II) after carried out the post-treatment, isolation and purification as mentioned above, may be allowed to react with a compound represented by the formula (VII) .
  • a compound represented by the formula (VII) it is appropriate without any post-treatment and the like of the trivalent hexadentate ortho-metallated iridium dinuclear complex to successively carry out the reaction of the complex represented by the formula (II) with a compound represented by the formula (VII) in one vessel (i.e., one-pot reaction) .
  • the compound represented by the formula (VII) and a base may be added separately into the reaction medium, or alternatively the compound of the formula (VII) may previously be allowed to react with a base and then added to the reaction medium.
  • a base for example, sodium acetylaceonate, potassium 2-acetylcyclohexanate, potassium benzoylacetonate, etc., may be used as a derivative from the compound of the formula (VII) .
  • the compound represented by the formula (VI) may be used usually in the amount appropriately selected from a range of 2 to 50 equivalents, preferably 3 to 20 equivalents, and more preferably 4 to 6 equivalents to the monovalent iridium dinuclear complex represented by the formula (I) .
  • amount of the compound representedby the formula (VII) may be used usually in the amount of 1 to 20 equivalents, preferably 1.5 to 10 equivalents, and more preferably 2 to 3 equivalents to the monovalent iridium dinuclear complex represented by the formula (I) .
  • the reaction is preferably carried out in the presence of a base.
  • a base an inorganic base and organic base are exemplified.
  • the inorganic base includes sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and metal hydrides such as sodium hydride and the like.
  • the organic base includes alkali metal alkoxides such as potassium methoxide, sodium methoxide, lithium methoxide, sodium ethoxide, and potassium tert-butoxide; and organic amines such as triethylamine, diisopropylethylamine, N,N-dimethylaniline, piperidine, pyridine, 4-dimethylaminopyridine,
  • alkali metal alkoxides such as potassium methoxide, sodium methoxide, lithium methoxide, sodium ethoxide, and potassium tert-butoxide
  • organic amines such as triethylamine, diisopropylethylamine, N,N-dimethylaniline, piperidine, pyridine, 4-dimethylaminopyridine,
  • An amount of the base may be used usually in the amount appropriately selected from a range of 0.5 to 10 equivalents, preferably 0.8 to 2 equivalents, and more preferably 1 to 1.2 equivalents to the compound of the formula (VII).
  • the reaction is preferably carried out in an atmosphere of inert gas such as nitrogen gas or argon gas. Also, this process may be carried out using an ultrasonic generator.
  • the reaction temperature is selected usually from the range of 25°C to 300°C, preferably from 60°C to 200°C, and more preferably from 80°C to 150°C.
  • the reaction time is selected usually from the range of 3 minutes to 48 hours, preferably 10 minutes to 24 hours, more preferably 30 minutes to 3 hours.
  • Scheme 3 illustrated the reaction sequence of a process for producing a trivalent hexadentate ortho-metallated iridiumcomplex representedbythe formula (IV) fromamonovalent iridium dinuclear complex represented by the formula (I) as a starting compound.
  • the trivalent hexadentate ortho-metallated iridium dinuclear complex represented by the formula (II) may readily be produced by reacting a monovalent iridium dinuclear complex represented by the formula (I) with a compound of the formula (VI) in or without a suitable solvent if required under an atmosphere of inert gas.
  • the resulting trivalent hexadentate ortho-metallated iridium dinuclear complex represented by the formula (II) is allowed to react with a compound represented by the formula (VIII) in or without a suitable solvent if required in the presence of a base, if required under an atmosphere of inert gas to smoothly give the trivalent hexadentate ortho-metallated iridium complex of the formula (IV).
  • the trivalent hexadentate ortho-metallated iridium dinuclear complex of the formula (II) after carried out the post-treatmnet, isolation andpurification as mentioned above, may be allowed to react with a compound represented by the formula (VIII) .
  • a compound represented by the formula (VIII) it is appropriate without any post-treatment of the trivalent hexadentate ortho-metallated iridium dinuclear complex to successively carry out the reaction of the complex of the formula (II) with a compound of the formula (VIII) in one vessel (i.e., one-pot reaction) .
  • the compound represented by the formula (VIII) and the base may be added separately into the reaction medium, or alternatively the compound of the formula (VIII) may previously be allowed to react with the base and then added to the reaction medium.
  • the compound of the formula (VIII) is first allowed to react with the base as mentioned below, for example, sodium picolinate, sodium 3-cyanopyridine-2-carboxylate, potassium 5-phenylpyridine-2-carboxylate, etc., may be used as a derivative from the compound of the formula (VIII) .
  • the compound represented by the formula (VI) may be used usually in the amount appropriately selected froma range of 2 to 50 equivalents, preferably 3 to 20 equivalents, andmore preferably 4 to 6 equivalents to the monovalent iridium dinuclear complex represented by the formula (I).
  • the compound of the formula (VIII) may be used usually in the amount of 1 to 20 equivalents, preferably 1.5 to 10 equivalents, and more preferably 2 to 3 equivalents to the monovalent iridium dinuclear complex of the formula (I) .
  • the reaction is preferably carried out in the presence of a base.
  • a base those as exemplified in Scheme 2 may be used.
  • the reaction is preferably carried out in an atmosphere of inert gas such as nitrogen gas, argon gas, and so on.
  • inert gas such as nitrogen gas, argon gas, and so on.
  • the reaction may also be carried out in combination with an ultrasonic generator.
  • the reaction temperature is selected usually from the range of 25°C to 300°C, preferably from 60°C to 200°C, and more preferably from 80°C to 150°C.
  • the reaction time is selected usually from the range of 3 minutes to 48 hours, preferably 10 minutes to 24 hours, more preferably 30 minutes to 3 hours.
  • Scheme 4 illustrates the reaction formula of aprocess for producing a trivalent hexadentate ortho-metallated iridium dinuclear complex represented by the formula (V) from a monovalent iridiumdinuclear complex representedby the formula
  • the trivalent hexadentate ortho-metallated iridium dinuclear complex represented by the formula (II) may readily be produced by reacting a monovalent iridium dinuclear complex represented by the formula (I) with a compound of the formula (VI) in or without a suitable solvent if required under an atmosphere of inert gas.
  • the resulting trivalent hexadentate ortho-metallated iridium dinuclear complex of the formula (II) is allowed to react with a compound of the formula (VI) and a silver salt in or without a suitable solvent if required under an atmosphere of inert gas to smoothly give the trivalent hexadentate ortho-metallated iridium complex of the formula (V) .
  • the trivalent hexadentate ortho-metallated iridium dinuclear complex of the formula (II), after carried out the post-treatment, isolation andpurification as mentioned above, may be allowed to react with a silver salt and a compound of the formula (VI) .
  • the compound represented by the formula (I) is first allowed to react with a compound represented by the formula (VI), to which a silver salt is then added, and then the compound of the formula (VI) is added to continue the reaction.
  • the silver salt includes, for example, silver nitrate, silver acetate, silver trifluoroacetate, silver methane- sulfonate, silver trifluoromethanesulfonate, and the like, with silver trifluoroacetate or silver trifluoromethanesulfonate being preferred.
  • the silver salt may be used usually in the amount of 1 to 20 equivalents, preferably 1.5 to 10 equivalents, and more preferably 2 to 3 equivalents to the compound represented by the formula (I) .
  • (VI) may be used usually in the amount appropriately selected from a range of 4 to 100 equivalents, preferably 6 to 40 equivalents, and more preferably 8 to 12 equivalents to the monovalent iridium dinuclear complex representedby the formula
  • the compound of the formula (VI) may be added usually in the amount appropriately selected from a range of 2 to 50 equivalents, preferably 3 to 10 equivalents, and more preferably 4 to 6 equivalents to the compound represented by the formula (I) .
  • the reaction is preferably carried out in an atmosphere of inert gas such as nitrogen gas, argon gas, and so on.
  • inert gas such as nitrogen gas, argon gas, and so on.
  • the reaction may also be carried out in combination with an ultrasonic generator.
  • reaction temperature is selected usually from the range of 25°C to 300°C, preferably from 60°C to 200°C, and more preferably from 80°C to 150°C.
  • reaction time is selected usually from the range of 10 minutes to 72 hours, preferably 30 minutes to 48 hours, more preferably 1 hour to 6 hours.
  • the process of the present invention is characterized in that the monovalent iridium dinuclear complexes are used.
  • the trivalent hexadentate ortho-metallated iridium complexes representedby the formula (II), (III), (IV) or (V) can be produced in high efficiency, and in addition it becomes possible to produce them in one-pot process without isolating the intermediate trivalent hexadentate ortho-metallated iridium dinuclear complexes of the formula (II) .
  • the process of the present invention is characterized by the followings.
  • the multi-step reaction can be carried out in the same reaction vessel and in the same solvent.
  • trivalent hexadentate ortho-metallated iridium complexes produced by the processes of the invention are useful as phosphorescent materials.
  • s/s indicates the volume ratio of the solvent to the weight of the starting monovalent iridium dinuclear complex in the unit of mL/g.
  • the reddish suspension turned into ocher and then into a reddish solution as the dissolution of the ligand by heating, which gave an yellow suspension with stirring.
  • the reddish suspension turned into gray and then into a dark reddish solution as the dissolution of the ligand by heating, which gave an lemon yellow suspension with stirring.
  • the resulting lemon yellow suspension was cooled to room temperature, to which were added acetylacetone (230 ⁇ L, 2.232 mmol, 3.0 equivalents) and sodium carbonate (237 mg, 2.232 mmol, 3.0 equivalents) successively, and further stirred under refluxing for 2 hours to give an yellow suspension.
  • the solvent was distilled off fromthe reactionmixture under reducedpressure, andthe residue was purified by silica gel column chromatography (eluent: dichloromethane) . The column fractions were condensed, and recrystallized from hexane/dichloromethane to give 896 mg of the title compound (3-10) as lemon yellow powder in 78.9%.
  • Example 6 (1) Since the yield was 78.9% in Example 6 (1), the process of the invention was recognized to be suitable for large-scale production.
  • the resulting yellow suspension was cooled to room temperature, to which were added acetylacetone (230 ⁇ L, 2.232 mmol, 3.0 equivalents) and sodium carbonate (237 mg, 2.232 mmol, 3.0 equivalents) successively, and further stirred for 3 hours to give an ocher suspension.
  • the solvent was distilled off from the reaction mixture under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: dichloromethane) . The column fractions were condensed, the resulting yellow solid was and recrystallized from hexane/dichloromethane to give 736 mg of the title compound (3-9) as yellow powder.
  • Example 10 Production of Compound (4-2) (Bis [2- (2, 4-difluorophenyl) pyridinato-N, C 6 '] iridium (III) picolinate)
  • the resulting lemon yellow suspension was cooled to room temperature, to which was added sodium picolinate (324 mg, 2.232 mmol, 3.0 equivalents), and further stirred under refluxing for 3 hours. The suspension slowly turn into orange with proceeding of the reaction.
  • Example 11 Total yield from Example 1 was 79.9%. When this step was carried out in one vessel, the total yield in Example 11 was 85.9% (see Example 11) . This indicates that the process of the invention can beneficially be conducted in one vessel.

Abstract

La présente invention concerne un procédé permettant de produire un complexe d'iridium ortho-métallé hexadentate trivalent avec un composé d'iridium et un composé de coordination en tant que produits de départ, lequel procédé se caractérise par l'utilisation d'un complexe binuléaire d'iridium monovalent représenté par la formule générale (I):(dans cette formule, A représente un composé diène non conjugué; et X représente un atome d'halogène). Selon cette invention, il est possible de procéder aux réactions successives dans le même récipient de réaction (c'est-à-dire une réaction en pot unique) au moyen du complexe produit au cours du procédé susmentionné dans l'étape suivante sans isolation ni purification.
PCT/JP2003/014192 2002-11-12 2003-11-07 Production de complexes d'iridium WO2004043974A1 (fr)

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EP3428986A1 (fr) * 2004-07-07 2019-01-16 Universal Display Corporation Matériaux électroluminescents stables et efficaces
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US7399857B2 (en) 2005-03-31 2008-07-15 Eastman Kodak Company Synthesis of organometallic cyclometallated transition metal complexes
EP2036914A1 (fr) * 2005-06-30 2009-03-18 Koninklijke Philips Electronics N.V. Complexes métalliques électroluminescents
EP2036915A1 (fr) * 2005-06-30 2009-03-18 Koninklijke Philips Electronics N.V. Complexes métalliques électroluminescents
WO2007004113A3 (fr) * 2005-06-30 2007-10-11 Koninkl Philips Electronics Nv Complexes metalliques electroluminescents
US8039124B2 (en) 2005-06-30 2011-10-18 Koninklijke Philips Electronics N.V. Electro luminescent metal complexes
US8664396B2 (en) 2007-11-21 2014-03-04 Bio-Rad Laboratories, Inc. Photoluminescent metal complexes for protein staining
EP2217608A4 (fr) * 2007-11-21 2011-06-29 Bio Rad Laboratories Complexes de métaux photoluminescents pour une coloration de protéines
EP2217608A1 (fr) * 2007-11-21 2010-08-18 Bio-Rad Laboratories, Inc. Complexes de métaux photoluminescents pour une coloration de protéines
EP2075251A3 (fr) * 2007-12-31 2009-10-21 Gracel Display Inc. Nouveaux composés électroluminescents rouges et dispositif électroluminescent organique les utilisant
EP3424936A1 (fr) * 2012-08-07 2019-01-09 Merck Patent GmbH Complexe métallique
CN104520308A (zh) * 2012-08-07 2015-04-15 默克专利有限公司 金属络合物
WO2014023377A3 (fr) * 2012-08-07 2014-09-04 Merck Patent Gmbh Complexes métalliques
US11917901B2 (en) 2012-08-07 2024-02-27 Udc Ireland Limited Metal complexes
CN104870458A (zh) * 2012-12-21 2015-08-26 默克专利有限公司 金属络合物
CN104870460A (zh) * 2012-12-21 2015-08-26 默克专利有限公司 金属络合物
CN104870459A (zh) * 2012-12-21 2015-08-26 默克专利有限公司 金属络合物
CN104870459B (zh) * 2012-12-21 2018-06-26 默克专利有限公司 金属络合物
WO2014094960A1 (fr) * 2012-12-21 2014-06-26 Merck Patent Gmbh Complexes métalliques
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