WO2005108372A1 - Procede pour produire des complexes metalliques avec des composes de metaux liquides volatiles - Google Patents

Procede pour produire des complexes metalliques avec des composes de metaux liquides volatiles Download PDF

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Publication number
WO2005108372A1
WO2005108372A1 PCT/US2004/010505 US2004010505W WO2005108372A1 WO 2005108372 A1 WO2005108372 A1 WO 2005108372A1 US 2004010505 W US2004010505 W US 2004010505W WO 2005108372 A1 WO2005108372 A1 WO 2005108372A1
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WIPO (PCT)
Prior art keywords
compound
volatile liquid
group
liquid metal
compounds
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PCT/US2004/010505
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English (en)
Inventor
James E. Boone
John C. Prindle
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Albemarle Corporation
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Priority to PCT/US2004/010505 priority Critical patent/WO2005108372A1/fr
Priority to TW094110676A priority patent/TW200601892A/zh
Publication of WO2005108372A1 publication Critical patent/WO2005108372A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • C07D215/26—Alcohols; Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • C07D215/26—Alcohols; Ethers thereof
    • C07D215/30—Metal salts; Chelates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/186—Metal complexes of the light metals other than alkali metals and alkaline earth metals, i.e. Be, Al or Mg

Definitions

  • This invention relates to a process of producing metal complexes, such as 8-quinolinoline metal complexes, which can be useful as electroluminescent materials.
  • An organic light emitting device is generally constructed of layers of organic compounds between electrodes.
  • a typical arrangement of such a device is anode/electroluminescent material/cathode.
  • a standard electroluminescent material used in such devices is tris(8-hydroxyquinoline)aluminum ("Alq3"). See, e g., Appl. Phys Lett., 51, 913 (1987). Substituted 8-quinolinolaluminum and related complexes as well as other metal ligand complexes are also known for use in OLEDs.
  • electroluminescent materials are made by (i) reacting low volatility metal salts, such as aluminum carboxylates, alkoxides, and chlorides, with 8-hydroxyquinolinyl or similar compounds, and then (ii) purifying by sublimation.
  • low volatility metal salts such as aluminum carboxylates, alkoxides, and chlorides
  • the present invention provides a process for making metal complexes, which may be useful as electroluminescent materials.
  • the present invention provides a process for making metal complexes by reacting a volatile liquid metal compound having a melting point of less than about 50°C and a vapor pressure of greater than about 50 mmHg at 150°C with a compound comprising at least one hydroxyl (OH) group.
  • the reaction can occur in an organic solvent, such as toluene, or in the gas phase.
  • the volatile liquid metal compound may, for example, include metal compounds comprising at least one alkyl, halide, or hydride group, where the alkyl, halide, or hydride group(s) can be the same or different.
  • volatile liquid metal compounds include: metal alkyl compounds, metal halide compounds, metal hydride compounds, metal alkyl-halide compounds, metal alkyl-hydride compounds, metal halo-hydride compounds, and metal alkyl- halo-hydride compounds.
  • the metal alkyl compounds can, for example, include trimethylaluminum, triethylaluminum, and triisobutylaluminum.
  • the metal alkyl-hydride compounds can, for example, include dimethylaluminum hydride, diethylaluminum hydride, and diisobutylaluminum hydride.
  • the metal alkyl-halo compounds can, for example, include methylaluminum sesquichloride, dimethyaluminum chloride, and diethylaluminum chloride.
  • the volatile liquid metal compound preferably reacts quickly, and to the extent possible, completely, with the compound comprising at least one hydroxyl group, and produces light hydrocarbon byproducts that are generally removed easily from the crude reaction product, essentially leaving only the desired product and some unreacted ligand.
  • the volatile liquid metal compound may be distilled by conventional methods to high purity before reacting it with a compound comprising at least one hydroxyl group to produce a higher purity crude electroluminescent material.
  • compounds commonly used to synthesize metal complexes typically lack the volatility to be good candidates for purification by conventional distillation.
  • aluminum isopropoxide which is commonly used to synthesize Alq3 (see Synth, and React, in Inorganic and Metal-Organic Chemistry (1999), 29(10), 1747-1767; Indian J. Chem., Section A (1976), 14A(6), 408-9), has a reported melting point of 1 18°C and a vapor pressure of 5.25 mmHg at 145-150°C.
  • Other alcoholates and carboxylates employed have similar volatilities.
  • examples of volatile liquid metal compounds that may be used in the present invention are substantially more volatile and, hence, can be more easily purified by conventional distillation.
  • Trimethylaluminum 15 1490 Dimethylaluminum Chloride -21 1444 Triethylaluminum -46 168 Diethylaluminum Chloride -74 130 Methylaluminum Sesquichloride 23 923 Ethylaluminum Dichloride 31 181 Ethylaluminum Sesquichloride -21 149 Triisobutvlaluminum 1 128
  • the term "metal complex” defines compounds of the formula: M(L) X wherein M represents a metal, x represents an integer from 1 to the charge number of the metal cation, such as, for example, from 1 to 3, and L represents a ligand derived from a compound comprising at least one hydroxyl (OH) group, wherein L can be the same or different.
  • M represents a metal
  • x represents an integer from 1 to the charge number of the metal cation, such as, for example, from 1 to 3
  • L represents a ligand derived from a compound comprising at least one hydroxyl (OH) group, wherein L can be the same or different.
  • An example of a compound comprising at least one hydroxyl (OH) group is a compound represented by Formula I:
  • R,-R 6 are selected from the group consisting of hydrogen, halogen, alkyl, aryl, alkoxy, aryloxy, amino, amido and cyano.
  • the metal complex may, for example, include metals (M), such as aluminum, zinc and boron.
  • M metals
  • a particularly preferred metal is aluminum and a particularly preferred ligand is one in which R,-R 6 in formula I are hydrogen, such that when x is 3, the metal complex is Alq3, as shown in Formula II:
  • the term "compound comprising at least one hydroxyl (OH) group” defines compounds reactive with volatile liquid metal compounds used in the invention, wherein the hydrogen atom of the at least one hydroxyl group is active (i.e., can be removed), allowing for the formation of metal complexes produced by the invention.
  • Examples of such compounds include 3-(2-benzothiazolyl)-4-hydroxy-2H-l-benzopyran-2-one and 4-hydroxyacridine.
  • Preferred compounds include substituted and unsubstituted hydroxyquinolines, including the compound represented by Formula I.
  • substituted is meant compounds of a given structural class where at least one hydrogen atom is replaced by a different substituent, such as, for example, halogen, alkyl, aryl, alkoxy, aryloxy, amino, amido and cyano.
  • a particularly preferred compound is 8-hydroxyquinoline.
  • volatile liquid metal compound defines organometallic compounds with melting points less than about 50°C, and vapor pressures of greater than about 50 mmHg at 150°C, and having the general structure
  • R is a group that is reactive with the hydrogen moiety of the at least one hydroxyl group, and x represents an integer from 1 to the charge number of the metal cation, such as, for example, from 1 to 3.
  • R which can be the same or different, include alkyl, halide and hydride groups.
  • metal alkyl compounds describes, for example, volatile liquid metal compounds having hydrocarbon ligands, which may be the same or different, of the formula C x H y wherein x ranges from 1 to 8 and y ranges from 3 to 17.
  • hydrocarbon ligands which may be the same or different, of the formula C x H y wherein x ranges from 1 to 8 and y ranges from 3 to 17.
  • examples of such compounds include triisobutylaluminum, as well as trimethylaluminum of Formula III and triethylaluminum of Formula IV:
  • metal halide compounds describes volatile liquid metal compounds having halogen ligands (F, CI, Br, I) that may be the same or different.
  • metal hydride compounds describes volatile liquid metal compounds having hydrogen (H) ligands.
  • metal alkyl-halide compounds describes, for example, volatile liquid metal compounds having at least one hydrocarbon ligand of the formula C x H y , wherein x ranges from 1 to 8 and y ranges from 3 to 17, and at least one halogen ligand, wherein each of the hydrocarbon and halogen ligands can be the same or different. Examples of such compounds include methylaluminum sesquichloride and ethylaluminum sesquichloride, as well as dimethylaluminum chloride of Formula V and diethylaluminum chloride of Formula VI:
  • metal alkyl-hydride compounds describes, for example, volatile liquid metal compounds having at least one hydrocarbon ligand of the formula C ⁇ H y , wherein x ranges from 1 to 8 and y ranges from 3 to 17, and at least one hydrogen ligand, wherein the hydrocarbon ligands can be the same or different.
  • hydrocarbon ligands can be the same or different. Examples of such compounds include dimethylaluminum hydride, diethylaluminum hydride and diisobutylaluminum
  • metal halo-hydride compounds describes volatile liquid metal compounds having at least one halogen ligand, that may be the same or different, and at least one hydrogen ligand.
  • metal alkyl-halo-hydride compounds describes volatile liquid metal compounds having at least one hydrocarbon ligand of the formula C ⁇ H y , wherein x ranges from 1 to 8 and y ranges from 3 to 17, at least one halogen ligand, and at least one hydrogen ligand.
  • the volatile liquid metal compound preferably has a high degree of purity. Purification of the volatile liquid metal compound can be performed, for example, by conventional distillation.
  • trimethylaluminum purity can, for example, be at least about 99.99%), or even, for example, at least about 99.9999%) based upon the total weight of the volatile liquid metal compound and trace metals (/ ' e., 0.1 ppm total trace metals).
  • Electroluminescent materials produced from this electronic grade trimethylaluminum and, for example, a purified 8-hydroxyquinoline compound can be expected to contain substantially lower trace metals, thereby reducing or avoiding time consuming purification by sublimation.
  • the processes of the invention can be generally conducted with an excess of the compound comprising at least one hydroxyl (OH) group, such as where the molar ratio of the compound comprising at least one hydroxyl (OH) group to the volatile liquid metal compound ranges from about the charge number of the metal cation (x) to 1 to about 1 +x to 1, such as from about 3 to 1 to about 4 to 1 when the volatile liquid metal compound is a trialkyl aluminum compound.
  • wash steps can be used to remove the excess of the compound comprising at least one reactive hydroxyl group (OH), as described in the examples below.
  • product drying is performed to remove residual solvent.
  • the compound comprising at least one hydroxyl (OH) group is reacted in excess in order to ensure that all of the substituents on the volatile liquid metal compound are completely reacted with the compound comprising at least one reactive hydroxyl (OH) group. Complete reaction on all of the substituents on the volatile liquid metal compound helps minimize the occurrence of reaction by-products, since many volatile liquid metal compounds are reactive to oxygen and/or water which could be present during the washing and product drying steps.
  • the rate at which the volatile liquid metal compound is preferably added to the compound comprising at least one reactive hydroxyl (OH) group is a function of the rate at which the energy of reaction and any gaseous by-products can be removed.
  • the processes of the invention can be conducted neat, with, for example, a solvent that is inert to alkyls such as toluene, or in the gas phase.
  • a solvent that is inert to alkyls such as toluene, or in the gas phase.
  • Other solvents that may be used include any branched or straight-chain aliphatic hydrocarbons (e.g. hexane, heptane, isohexane), other aromatics (e.g. benzene), alkylated aromatics, or mixtures or any of these species (e.g.
  • distillate cuts from a refinery When conducted in the gas phase at temperatures below about 50°C, an inert carrier gas, such as nitrogen, can be used to volatilize both the volatile liquid metal compound and the compound comprising the at least one reactive hydroxyl (OH) group.
  • an inert carrier gas such as nitrogen
  • the processes of the invention can be conducted as a batch process or as a continuous process. These processes, whether batch or continuous, can, for example, be conducted at a temperature ranging from about 0°C to about 100°C, such as from about 0°C to about 50°C, and, for example, at pressures of up to about 1 atmosphere. Higher temperatures can generally be expected to result in increased formation of reaction by-product impurities whereas lower temperatures can result in the need for increased solvent in order to dissolve the compound comprising at least one hydroxyl (OH) group. However, when conducted in the gas phase, higher reaction temperatures, such as those in excess of 100°C, may result in suitably low quantities of by-product impurities due to the generally lower local concentrations of reactants in the gas phase.
  • the present invention provides a process of making Alq3 by reacting triethylaluminum of Formula IV with 8-hydroxyquinoline of formula VII:
  • this invention is not limited to 8-hydroxyquinolinyl or aluminum compounds.
  • This invention could also be applied to producing other metal complexes useful for OLED applications such as reacting a zinc dialkyl, such as diethylzinc, with ligands like 3-(2- benzothiazolyl)-4-hydroxy-2H-l-benzopyran-2-one or 4-hydroxyacridine.
  • ligands like 3-(2- benzothiazolyl)-4-hydroxy-2H-l-benzopyran-2-one or 4-hydroxyacridine.
  • a wide range of combinations can be produced in which a volatile liquid metal compound is reacted with a ligand having an active hydrogen.
  • the processes of the invention can, for example, result in products having a purity, based on the total weight of the metal complex product, of at least about 99.7%, such as at least about 99.9%), when measured by 'H-NMR.
  • a purity based on the total weight of the metal complex product, of at least about 99.7%, such as at least about 99.9%
  • the need for sublimation to further purify the reaction product to provide for suitable electroluminescent materials is either reduced or eliminated.
  • the amounts of such solvent and reactant impurities may generally be expected to constitute less than 0.1 %> by weight of the total metal complex product, when the washing and product drying steps following the reaction are conducted carefully.
  • potential non- organic impurities, such as trace metals can be expected to be relatively negligible (less than 1 ppm or 0.01 wt%o), provided that the starting volatile liquid metal compound is sufficiently pure.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)

Abstract

La présente invention concerne des procédés pour produire des complexes métalliques qui sont utiles dans des dispositifs luminescents organiques (OLEDs), les procédés comprenant la mise en réaction d'un composé de métal liquide volatile avec un composé qui comprend au moins un groupe hydroxyle (OH), tel qu'une 8-hydroxyquinoline. Des composés de métaux liquides volatiles sont par exemple triméthylaluminium, triéthylaluminium, triisobutylaluminium, hydrure de diisobutylaluminium, chlorure de diméthylaluminium, et chlorure de diéthylaluminium. Un complexe métallique utile qui peut être produit selon l'invention, est le tris(8-hydroxyquinoline)aluminium (Alq3).
PCT/US2004/010505 2004-04-05 2004-04-05 Procede pour produire des complexes metalliques avec des composes de metaux liquides volatiles WO2005108372A1 (fr)

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PCT/US2004/010505 WO2005108372A1 (fr) 2004-04-05 2004-04-05 Procede pour produire des complexes metalliques avec des composes de metaux liquides volatiles
TW094110676A TW200601892A (en) 2004-04-05 2005-04-04 Process to make metal complexes with volatile liquid metal compounds

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101003730B (zh) * 2006-11-07 2010-05-12 南昌大学 以八羟基喹啉为辅助配体的重金属配合物电致磷光材料及其合成方法
CN104151238A (zh) * 2014-07-30 2014-11-19 南昌航空大学 一种直接制备纯8-羟基喹啉铝的方法
CN115181064A (zh) * 2022-08-22 2022-10-14 生工生物工程（上海）股份有限公司 一种8-羟基喹啉的纯化方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000032717A1 (fr) * 1998-12-02 2000-06-08 South Bank University Enterprises Ltd. Quinolates electroluminescents
US20030030193A1 (en) * 2000-03-23 2003-02-13 Mahito Soeda Sublimation purifying method and apparatus
WO2004073030A2 (fr) * 2003-02-06 2004-08-26 Georgia Tech Research Corporation Polymeres fonctionalises de metal 8-hydroxyquinoleine, materiaux et procedes associes de fabrication et d'utilisation de ces derniers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000032717A1 (fr) * 1998-12-02 2000-06-08 South Bank University Enterprises Ltd. Quinolates electroluminescents
US20030030193A1 (en) * 2000-03-23 2003-02-13 Mahito Soeda Sublimation purifying method and apparatus
WO2004073030A2 (fr) * 2003-02-06 2004-08-26 Georgia Tech Research Corporation Polymeres fonctionalises de metal 8-hydroxyquinoleine, materiaux et procedes associes de fabrication et d'utilisation de ces derniers

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Katalog Handbuch Feinchemikalien und Laborgeräte 2003-2004", 2003, ALDRICH, XP002309934 *
ANONYMOUS: "Trimethylaluminum, Product No. 59,77-5, CAS Rn 75-24-1", INTERNET ARTICLE, XP002309618, Retrieved from the Internet <URL:http://www.sigmaaldrich.com/Brands/Fine_Chemicals/Product_Focus/Organics/Trimethylalu...> [retrieved on 20041203] *
HOPKINS, T. A. ET AL: "Substituted aluminum and zinc quinolates with blue-shifted absorbance/luminescence bands: synthesis and spectroscopic, photoluminescence, and electroluminescence characterization", CHEMISTRY OF MATERIALS , 8(2), 344-51 CODEN: CMATEX; ISSN: 0897-4756, 1996, XP002309620 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101003730B (zh) * 2006-11-07 2010-05-12 南昌大学 以八羟基喹啉为辅助配体的重金属配合物电致磷光材料及其合成方法
CN104151238A (zh) * 2014-07-30 2014-11-19 南昌航空大学 一种直接制备纯8-羟基喹啉铝的方法
CN115181064A (zh) * 2022-08-22 2022-10-14 生工生物工程（上海）股份有限公司 一种8-羟基喹啉的纯化方法

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