WO2014091974A1 - Light-emitting material - Google Patents

Light-emitting material Download PDF

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WO2014091974A1
WO2014091974A1 PCT/JP2013/082534 JP2013082534W WO2014091974A1 WO 2014091974 A1 WO2014091974 A1 WO 2014091974A1 JP 2013082534 W JP2013082534 W JP 2013082534W WO 2014091974 A1 WO2014091974 A1 WO 2014091974A1
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compound
formula
platinum complex
carbon atoms
platinum
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PCT/JP2013/082534
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French (fr)
Japanese (ja)
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直田健
小宮成義
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国立大学法人大阪大学
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    • 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
    • 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
    • C07F15/0086—Platinum compounds
    • C07F15/0093—Platinum compounds without a metal-carbon linkage
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
    • 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • 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
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
    • 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
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd

Definitions

  • the present invention relates to a light emitting material containing a platinum complex and the platinum complex.
  • Phosphorescent light emission by an organometallic complex can achieve a theoretically higher quantum efficiency than fluorescent light emission in organic EL (electroluminescence).
  • the said organometallic complex is anticipated as a material of functional elements, such as an organic light emitting element which is a next generation technique, specifically, a material of an organic EL display, etc.
  • PL (photoluminescence) compounds that exhibit strong solid-state light emission (crystal light emission) by ultraviolet light excitation is expected from the viewpoint of functional materials in the future.
  • organic platinum complexes have been attracting attention as phosphorescent materials as organometallic complexes.
  • an organic platinum complex containing a platinum atom coordinated with two NN type bidentate ligands or two NO type bidentate ligands is known (for example, Patent Document 1).
  • An organic platinum complex containing a platinum atom coordinated by a tetradentate ligand is also known (for example, Patent Document 2).
  • platinum complex A coordinated by ppy (phenylpyridine) and acac (acetylacetonate)
  • Patent Document 3 Non-Patent Document 1
  • platinum complexes have been reported to emit light in solution or in a low concentration dispersion state.
  • these platinum complexes are molecules with high planarity, they emit light in a high density state like crystals. The strength is considered weak.
  • an object of the present invention is to provide a light emitting material that is solid and has high emission intensity.
  • the present invention is a light emitting material containing a platinum complex represented by the formula (I).
  • n is an integer of 7 to 25, and R is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms.
  • the present invention is a platinum complex represented by the formula (X).
  • n is an integer of 7 to 11 or 13 to 25, and R ′ is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, or m is 12 and R ′ is an alkoxy group having 1 to 6 carbon atoms.
  • the light emitting material containing the platinum complex of the present invention is solid and has an advantage of high emission intensity.
  • FIG. 1 is a powder X-ray diffraction (XRD) diagram of the compound (1) of Example 1.
  • FIG. FIG. 2 is a powder X-ray diffraction (XRD) diagram of the compound (2) of Example 2.
  • FIG. 3 is a powder X-ray diffraction (XRD) diagram of the compound (3) of Example 3.
  • 4 is a powder X-ray diffraction (XRD) diagram of the compound (4) of Example 4.
  • FIG. 5 is a powder X-ray diffraction (XRD) diagram of the compound (5) of Example 5.
  • FIG. 6 is an XRD pattern obtained by simulation from the single crystal X-ray analysis result of the compound (11) of Comparative Example 1.
  • FIG. 7 is a diagram of an XRD pattern obtained by simulation from the single crystal X-ray analysis result of the compound (12) of Comparative Example 2.
  • FIG. 8 is a packing diagram in the crystal of the compound (2) of Example 2.
  • FIG. 9 is a packing diagram in the crystal of the compound (11) of Comparative Example 1.
  • FIG. 10 is a packing diagram in the crystal of the compound (12) of Comparative Example 2.
  • the present inventors have used bis (iminophenoxy) platinum as a mother skeleton, and when a chain alkyl group having a specific number of carbon atoms is substituted for an imino nitrogen atom, strong emission intensity is obtained in a high-density solid state such as a crystal. Unexpectedly found to show. Specifically, it has been found that in the following formula (I), when n is 7 or more, a lamellar structure in which molecules are arranged in layers in the crystal is formed, and as a result, the emission intensity is increased. On the other hand, it has also been found that when n is as short as 5 or less in the following formula (I), the lamellar structure is not taken in the crystal, and as a result, the emission intensity does not increase. Based on these findings, the present inventors have completed the present invention.
  • the platinum complex in the luminescent material of the present invention is represented by the following formula (I).
  • n is an integer of 7 to 25, and R is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms.
  • substitution position of R may be any of position a, position b, position c, and position d shown in the following formula. Note that the position a, the position b, the position c, and the position d may be referred to as the third, fourth, fifth, and sixth positions, respectively.
  • n is an integer of 7 to 25
  • R is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms
  • R is b Is a platinum complex of the formula (I) that binds to the position (position 4).
  • n is an integer of 8 to 18
  • R is a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms
  • R is the position of b (position 4).
  • the platinum complex in the light emitting material of the present invention is preferably a compound represented by the following formula, for example.
  • the platinum complex represented by the formula (I) preferably has a lamellar structure in single crystal X-ray structure analysis.
  • the platinum complex of the present invention is represented by the following formula (X).
  • n is an integer of 7 to 11 or 13 to 25, and R ′ is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, or m is 12 and R ′ is an alkoxy group having 1 to 6 carbon atoms.
  • substitution position of R ′ may be any of position a, position b, position c, and position d shown in the formula, similarly to the substituent of R in formula (I). Note that the position a, the position b, the position c, and the position d may be referred to as the third, fourth, fifth, and sixth positions, respectively.
  • m is an integer of 7 to 11 or 13 to 25
  • R ′ is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
  • Is a platinum complex of the formula (I) bonded to the position b (position 4), and m is 12, and R ′ is an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
  • R ′ is preferably a platinum complex of the formula (X) in which the position b (position 4) is bonded.
  • the platinum complex of the present invention is more preferably a platinum complex of the formula (X) in which m is an integer of 7 to 11 or 13 to 19 and R ′ is a hydrogen atom, and m is 8 to 11 or 13 More preferred is a platinum complex of the formula (X) which is an integer of ⁇ 18 and R ′ is a hydrogen atom. This is because such a platinum complex exhibits strong emission intensity.
  • the platinum complex of the present invention is more preferably a platinum complex of the formula (X) in which m is an integer of 7 to 19 and R ′ is an alkoxy group having 1 to 6 carbon atoms, and m is 7 to More preferred is a platinum complex of the formula (X) which is an integer of 19 and R ′ is an alkoxy group having 1 to 6 carbon atoms, and R ′ is bonded to the position (position 4) of b. This is because such a platinum complex exhibits strong emission intensity.
  • the platinum complex of the present invention is preferably a compound represented by the following formula, for example.
  • the platinum complex of the light emitting material of the present invention can be produced, for example, as follows.
  • n and R are as defined in formula (I).
  • a compound of formula (I) is reacted with a platinum compound in the presence of a base to give a compound of formula (I).
  • platinum compound examples include PtCl 2 (CH 3 CN) 2 and K 2 PtCl 4 .
  • the base for example, K 2 CO 3 , NaH, triethylamine or the like may be used. This reaction is carried out, for example, at 20 to 120 ° C. for 1 to 48 hours.
  • the solvent for this reaction include, but are not limited to, a mixture of dimethylformamide (DMF) and methanol, dimethyl sulfoxide (DMSO), and the like.
  • the compound of the formula (I) may be recrystallized from, for example, a mixture of an aromatic hydrocarbon and an aliphatic hydrocarbon.
  • the aromatic hydrocarbon include benzene and toluene.
  • the aliphatic hydrocarbon include aliphatic hydrocarbons having 5 to 7 carbon atoms, among which n-hexane is preferable.
  • the mixing ratio (volume ratio) of the aromatic hydrocarbon and the aliphatic hydrocarbon is, for example, 1: 1 to 10, and preferably 4: 6.
  • the compound represented by the formula (II) may be obtained commercially, or may be made in-house with reference to known literature.
  • the compound represented by the formula (II) can be produced, for example, as follows.
  • n and R are as defined in formula (I).
  • a compound of formula (II) is obtained by heating a salicylaldehyde derivative of formula (III) and 1 equivalent of an amine (compound of formula (IV)) in a solvent. This reaction is carried out, for example, at 20 to 100 ° C. for the necessary time.
  • the solvent for this reaction include, but are not limited to, methanol, a mixture of dimethylformamide (DMF) and methanol, dimethyl sulfoxide (DMSO), and the like.
  • the platinum complex represented by the formula (X) of the present invention can be produced in the same manner as the platinum complex represented by the formula (I).
  • the light emitting material of the present invention can be used as a light emitting material of an organic EL element, specifically, a material of a light emitting layer.
  • an organic EL element for example, a substrate, an anode, a hole transport layer, a light emitting layer containing the light emitting material of the present invention, an electron transport layer, and a cathode are laminated in this order.
  • the substrate, the anode, the hole transport layer, the electron transport layer, and the cathode may be formed by a conventionally known manufacturing method using a conventionally known material.
  • the light emitting layer may contain a host material in addition to the light emitting material of the present invention.
  • the host material include those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an arylsilane skeleton.
  • the quantum yield was measured using a fluorometer FP-6500N, a low-temperature medium integrating sphere system INK-533 for phosphorescence measurement, and a liquid sample cell LPH-120 (all manufactured by JASCO Corporation).
  • Example 1 Compound (1), Example 2 Compound (2), Example 3 Compound (3), Example 4 Compound (4), Example 5 Compound (5) and Comparative Example 1
  • the compound (1) of Example 1, the compound (2) of Example 2, the compound (3) of Example 3, the compound (4) of Example 4 and the compound (5) of Example 5 were heated.
  • the XRD pattern of the obtained compound (1) of Example 1 is shown in FIG. 1
  • the XRD pattern of the compound (2) of Example 2 is shown in FIG. 2
  • the XRD pattern of the compound (3) of Example 3 is shown in FIG.
  • the XRD pattern of the compound (4) of Example 4 is shown in FIG. 4
  • the XRD pattern of the compound (5) of Example 5 is shown in FIG. 5
  • the single crystal X-ray structural analysis result of the compound (11) of Comparative Example 1 is shown in FIG.
  • FIG. 6 shows an XRD pattern obtained by simulation
  • FIG. 7 shows an XRD pattern obtained by simulation from the single crystal X-ray structural analysis result of the compound (12) of Comparative Example 2.
  • FIG. 8 shows a packing diagram in the crystal of the compound (2) of Example 2 obtained as a result of the obtained crystal analysis
  • FIG. 9 shows a packing diagram in the crystal of the compound (11) of Comparative Example 1
  • FIG. 10 shows a packing diagram of the compound (12) of 2 in the crystal.
  • the platinum complex of the example has a lamellar structure in which molecules are arranged in layers in a crystal and have a lattice spacing (d) corresponding to the number of n (length of alkyl chain). It was confirmed that the structure was adopted. On the other hand, as shown in FIGS. 6 and 7, it was confirmed that the platinum complex of the comparative example did not have such a lamellar structure.
  • the molecular arrangement in the crystal has a lamellar structure.
  • the compound represented by the formula (I) does not quench between molecules in a crystalline state, it is considered that strong intensity phosphorescence can be realized.
  • the light emitting material of the present invention is solid and has excellent light emission efficiency, it is possible to obtain light emission intensity sufficient for practical use. Therefore, the light-emitting material of the present invention is useful as a material for organic light-emitting elements that are the next generation technology.

Abstract

The present invention addresses the problem of providing a light-emitting material that is a solid and has a high emission intensity. A light-emitting material containing a platinum complex that can be represented by formula (I). (I) (In the formula, n represents an integer from 7 to 25 and R represents either a hydrogen atom or a C1-6 alkoxy group.)

Description

発光材料Luminescent material
　本発明は、白金錯体を含む発光材料、および、その白金錯体に関する。 The present invention relates to a light emitting material containing a platinum complex and the platinum complex.
　有機金属錯体による燐光性の発光は、有機ＥＬ（エレクトロルミネッセンス）において蛍光性の発光よりも理論的に高い量子効率を達成することが可能である。このため、当該有機金属錯体は、例えば次世代技術である有機発光素子等の機能素子の材料、具体的には有機ＥＬディスプレイの材料等として期待されている。
　また、紫外光励起により強い固体発光（結晶発光）を示すＰＬ（フォトルミネッセンス）化合物は、将来の機能性材料の観点からその開発が期待されている。 Phosphorescent light emission by an organometallic complex can achieve a theoretically higher quantum efficiency than fluorescent light emission in organic EL (electroluminescence). For this reason, the said organometallic complex is anticipated as a material of functional elements, such as an organic light emitting element which is a next generation technique, specifically, a material of an organic EL display, etc.
In addition, development of PL (photoluminescence) compounds that exhibit strong solid-state light emission (crystal light emission) by ultraviolet light excitation is expected from the viewpoint of functional materials in the future.
　近年、有機金属錯体として有機白金錯体が燐光発光材料として着目されてきている。例えば、２個のＮＮ型二座配位子または２個のＮＯ型二座配位子が配位した白金原子を含む有機白金錯体が知られている（例えば、特許文献１）。また、四座配位子が配位した白金原子を含む有機白金錯体も知られている（例えば、特許文献２）。 In recent years, organic platinum complexes have been attracting attention as phosphorescent materials as organometallic complexes. For example, an organic platinum complex containing a platinum atom coordinated with two NN type bidentate ligands or two NO type bidentate ligands is known (for example, Patent Document 1). An organic platinum complex containing a platinum atom coordinated by a tetradentate ligand is also known (for example, Patent Document 2).
　また、白金に２種類の配位子を有する非対称型錯体として、たとえば、ppy(フェニルピリジン)、acac(アセチルアセトナート)が配位した白金錯体Ａ（特許文献３、非特許文献１）が知られている。これらの白金錯体は、溶液や低濃度分散状態で発光することが報告されているが、しかし、これらの白金錯体は、平面性の高い分子であることから、結晶のような高密度状態では発光強度は弱いと考えられる。 Further, as an asymmetric complex having two kinds of ligands in platinum, for example, platinum complex A coordinated by ppy (phenylpyridine) and acac (acetylacetonate) (Patent Document 3, Non-Patent Document 1) is known. It has been. These platinum complexes have been reported to emit light in solution or in a low concentration dispersion state. However, since these platinum complexes are molecules with high planarity, they emit light in a high density state like crystals. The strength is considered weak.
特開２００７－５３５８０７号公報JP 2007-535807 A 特開２００９－２２４７６３号公報JP 2009-224763 A 特開２００７－１６１８８６号公報JP 2007-161886 A
　そこで、本発明は、固体であって、発光強度が強い発光材料を提供することを目的とする。 Therefore, an object of the present invention is to provide a light emitting material that is solid and has high emission intensity.
　本発明は、式（Ｉ）で表される白金錯体を含む発光材料である。 The present invention is a light emitting material containing a platinum complex represented by the formula (I).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
［前記式中、ｎは、７～２５の整数であり、かつＲは、水素原子または炭素数１～６を有するアルコキシ基である。］ [In the above formula, n is an integer of 7 to 25, and R is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms. ]
　また、本発明は、式（Ｘ）で表される白金錯体である。 Further, the present invention is a platinum complex represented by the formula (X).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　［前記式中、ｍは、７～１１または１３～２５の整数であり、かつＲ’は、水素原子または炭素数１～６を有するアルコキシ基であるか、または、
ｍは、１２であり、かつＲ’は、炭素数１～６を有するアルコキシ基である。］ [Wherein, m is an integer of 7 to 11 or 13 to 25, and R ′ is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, or
m is 12 and R ′ is an alkoxy group having 1 to 6 carbon atoms. ]
　本発明の白金錯体を含む発光材料は、固体であって、発光強度が強いという利点がある。 The light emitting material containing the platinum complex of the present invention is solid and has an advantage of high emission intensity.
図１は、実施例１の化合物（１）の粉末Ｘ線回折（ＸＲＤ）の図である。1 is a powder X-ray diffraction (XRD) diagram of the compound (1) of Example 1. FIG. 図２は、実施例２の化合物（２）の粉末Ｘ線回折（ＸＲＤ）の図である。FIG. 2 is a powder X-ray diffraction (XRD) diagram of the compound (2) of Example 2. 図３は、実施例３の化合物（３）の粉末Ｘ線回折（ＸＲＤ）の図である。FIG. 3 is a powder X-ray diffraction (XRD) diagram of the compound (3) of Example 3. 図４は、実施例４の化合物（４）の粉末Ｘ線回折（ＸＲＤ）の図である。4 is a powder X-ray diffraction (XRD) diagram of the compound (4) of Example 4. FIG. 図５は、実施例５の化合物（５）の粉末Ｘ線回折（ＸＲＤ）の図である。5 is a powder X-ray diffraction (XRD) diagram of the compound (5) of Example 5. FIG. 図６は、比較例１の化合物（１１）の単結晶Ｘ線解析結果からシミュレーションにより求めたＸＲＤパターンの図である。6 is an XRD pattern obtained by simulation from the single crystal X-ray analysis result of the compound (11) of Comparative Example 1. FIG. 図７は、比較例２の化合物（１２）の単結晶Ｘ線解析結果からシミュレーションにより求めたＸＲＤパターンの図である。FIG. 7 is a diagram of an XRD pattern obtained by simulation from the single crystal X-ray analysis result of the compound (12) of Comparative Example 2. 図８は、実施例２の化合物（２）の結晶中におけるパッキング図である。FIG. 8 is a packing diagram in the crystal of the compound (2) of Example 2. 図９は、比較例１の化合物（１１）の結晶中におけるパッキング図である。FIG. 9 is a packing diagram in the crystal of the compound (11) of Comparative Example 1. 図１０は、比較例２の化合物（１２）の結晶中におけるパッキング図である。FIG. 10 is a packing diagram in the crystal of the compound (12) of Comparative Example 2.
　本発明者らは、ビス（イミノフェノキシ）白金を母骨格とし、イミノ窒素原子に、特定の炭素数の鎖状アルキル基を置換させると、結晶のような高密度の固体状態で強い発光強度を示すことを予想外に見出した。具体的には、下記式（Ｉ）において、ｎが７以上であれば、結晶中において分子が層状に並んだラメラ構造をとり、その結果、発光強度が強くなることを見出した。一方、下記式（Ｉ）においてｎが５以下と短い場合、結晶中において前記ラメラ構造をとらず、その結果、発光強度は強くならないことも見出した。これらの知見に基づき、本発明者らは、本発明を完成した。 The present inventors have used bis (iminophenoxy) platinum as a mother skeleton, and when a chain alkyl group having a specific number of carbon atoms is substituted for an imino nitrogen atom, strong emission intensity is obtained in a high-density solid state such as a crystal. Unexpectedly found to show. Specifically, it has been found that in the following formula (I), when n is 7 or more, a lamellar structure in which molecules are arranged in layers in the crystal is formed, and as a result, the emission intensity is increased. On the other hand, it has also been found that when n is as short as 5 or less in the following formula (I), the lamellar structure is not taken in the crystal, and as a result, the emission intensity does not increase. Based on these findings, the present inventors have completed the present invention.
　本発明の発光材料における白金錯体は、以下の式（Ｉ）で表される。 The platinum complex in the luminescent material of the present invention is represented by the following formula (I).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
［前記式中、ｎは、７～２５の整数であり、かつＲは、水素原子または炭素数１～６を有するアルコキシ基である。］ [In the above formula, n is an integer of 7 to 25, and R is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms. ]
　なお、Ｒの置換位置は、下記式中に示す位置ａ、位置ｂ、位置ｃ、位置ｄのうち、いずれであってもよい。なお、位置ａ、位置ｂ、位置ｃおよび位置ｄは、それぞれ、３位、４位、５位および６位とも呼ぶことがある。 Note that the substitution position of R may be any of position a, position b, position c, and position d shown in the following formula. Note that the position a, the position b, the position c, and the position d may be referred to as the third, fourth, fifth, and sixth positions, respectively.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　本発明の発光材料における白金錯体は、ｎが、７～２５の整数であり、かつＲが、水素原子または炭素数１～６、好ましくは１～３を有するアルコキシ基であり、Ｒが前記ｂの位置（４位）に結合する式（Ｉ）の白金錯体である。 In the platinum complex in the luminescent material of the present invention, n is an integer of 7 to 25, and R is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and R is b Is a platinum complex of the formula (I) that binds to the position (position 4).
　また、本発明の発光材料における白金錯体は、ｎが８～１８の整数であり、かつＲは水素原子または炭素数１～３を有するアルコキシ基であり、Ｒが前記ｂの位置（４位）に結合する式（Ｉ）の白金錯体が好ましい。 In the platinum complex in the luminescent material of the present invention, n is an integer of 8 to 18, R is a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms, and R is the position of b (position 4). Preference is given to platinum complexes of the formula (I) which bind to
　また、本発明の発光材料における白金錯体は、例えば、以下の式で表される化合物が好ましい。 In addition, the platinum complex in the light emitting material of the present invention is preferably a compound represented by the following formula, for example.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　また、本発明の発光材料は、単結晶Ｘ線構造解析において、式（Ｉ）で表される白金錯体が、ラメラ構造をとるのが好ましい。 In the luminescent material of the present invention, the platinum complex represented by the formula (I) preferably has a lamellar structure in single crystal X-ray structure analysis.
　また、本発明の白金錯体は、以下の式（Ｘ）で表される。 The platinum complex of the present invention is represented by the following formula (X).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　［前記式中、ｍは、７～１１または１３～２５の整数であり、かつＲ’は、水素原子または炭素数１～６を有するアルコキシ基であるか、または、
ｍは、１２であり、かつＲ’は、炭素数１～６を有するアルコキシ基である。］ [Wherein, m is an integer of 7 to 11 or 13 to 25, and R ′ is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, or
m is 12 and R ′ is an alkoxy group having 1 to 6 carbon atoms. ]
　なお、Ｒ’の置換位置は、式（Ｉ）におけるＲの置換基と同様、式中に示す位置ａ、位置ｂ、位置ｃ、位置ｄのうち、いずれであってもよい。なお、位置ａ、位置ｂ、位置ｃおよび位置ｄは、それぞれ、３位、４位、５位および６位とも呼ぶことがある。 In addition, the substitution position of R ′ may be any of position a, position b, position c, and position d shown in the formula, similarly to the substituent of R in formula (I). Note that the position a, the position b, the position c, and the position d may be referred to as the third, fourth, fifth, and sixth positions, respectively.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　本発明の白金錯体は、ｍが、７～１１または１３～２５の整数であり、かつＲ’が、水素原子または炭素数１～６、好ましくは１～３を有するアルコキシ基であり、Ｒ’が前記ｂの位置（４位）に結合する式（Ｉ）の白金錯体、およびｍは、１２であり、かつＲ’は、炭素数１～６、好ましくは１～３を有するアルコキシ基であり、Ｒ’が前記ｂの位置（４位）に結合する式（Ｘ）の白金錯体が好ましい。 In the platinum complex of the present invention, m is an integer of 7 to 11 or 13 to 25, and R ′ is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Is a platinum complex of the formula (I) bonded to the position b (position 4), and m is 12, and R ′ is an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. , R ′ is preferably a platinum complex of the formula (X) in which the position b (position 4) is bonded.
　また、本発明の白金錯体は、ｍが７～１１または１３～１９の整数であり、かつ、Ｒ’が水素原子である式（Ｘ）の白金錯体がより好ましく、ｍが８～１１または１３～１８の整数であり、かつ、Ｒ’が水素原子である式（Ｘ）の白金錯体がさらに好ましい。このような白金錯体であれば、強い発光強度を示すからである。 The platinum complex of the present invention is more preferably a platinum complex of the formula (X) in which m is an integer of 7 to 11 or 13 to 19 and R ′ is a hydrogen atom, and m is 8 to 11 or 13 More preferred is a platinum complex of the formula (X) which is an integer of ˜18 and R ′ is a hydrogen atom. This is because such a platinum complex exhibits strong emission intensity.
　また、本発明の白金錯体は、ｍが７～１９の整数であり、かつ、Ｒ’が炭素数１～６を有するアルコキシ基である式（Ｘ）の白金錯体がより好ましく、ｍが７～１９の整数であり、かつ、Ｒ’が炭素数１～６を有するアルコキシ基であり、Ｒ’が前記ｂの位置（４位）に結合する式（Ｘ）の白金錯体がさらに好ましい。このような白金錯体であれば、強い発光強度を示すからである。 The platinum complex of the present invention is more preferably a platinum complex of the formula (X) in which m is an integer of 7 to 19 and R ′ is an alkoxy group having 1 to 6 carbon atoms, and m is 7 to More preferred is a platinum complex of the formula (X) which is an integer of 19 and R ′ is an alkoxy group having 1 to 6 carbon atoms, and R ′ is bonded to the position (position 4) of b. This is because such a platinum complex exhibits strong emission intensity.
　また、本発明の白金錯体は、例えば、以下の式で表される化合物が好ましい。 In addition, the platinum complex of the present invention is preferably a compound represented by the following formula, for example.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　本発明の発光材料の白金錯体は、例えば、以下のようにして製造することができる。 The platinum complex of the light emitting material of the present invention can be produced, for example, as follows.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　前記式中、ｎおよびＲは、式（Ｉ）における定義と同様である。 In the above formula, n and R are as defined in formula (I).
　式（ＩＩ）の化合物と、白金化合物とを、塩基存在下に反応させて式（Ｉ）の化合物を得る。この白金化合物としては、例えば、ＰｔＣｌ2（ＣＨ3ＣＮ）2、Ｋ2ＰｔＣｌ4が挙げられる。塩基としては、例えばＫ2ＣＯ3、ＮａＨ、トリエチルアミン等を用いてもよい。この反応は、例えば２０～１２０℃で、１時間～４８時間、行う。この反応の溶媒としては、限定されないが、例えば、ジメチルホルムアミド（ＤＭＦ）とメタノールの混合物、ジメチルスルホキシド（ＤＭＳＯ）等が挙げられる。 A compound of formula (I) is reacted with a platinum compound in the presence of a base to give a compound of formula (I). Examples of the platinum compound include PtCl 2 (CH 3 CN) 2 and K 2 PtCl 4 . As the base, for example, K 2 CO 3 , NaH, triethylamine or the like may be used. This reaction is carried out, for example, at 20 to 120 ° C. for 1 to 48 hours. Examples of the solvent for this reaction include, but are not limited to, a mixture of dimethylformamide (DMF) and methanol, dimethyl sulfoxide (DMSO), and the like.
　前記式（Ｉ）の化合物は、例えば、芳香族炭化水素と脂肪族炭化水素との混合物から再結晶してもよい。前記芳香族炭化水素としては、例えば、ベンゼン、トルエンが挙げられる。前記脂肪族炭化水素としては、例えば、炭素数５～７の脂肪族炭化水素が挙げられ、中でも、ｎ－ヘキサンが好ましい。前記芳香族炭化水素と前記脂肪族炭化水素の混合比（体積比）は、例えば、１：１～１０であり、４:６が好ましい。 The compound of the formula (I) may be recrystallized from, for example, a mixture of an aromatic hydrocarbon and an aliphatic hydrocarbon. Examples of the aromatic hydrocarbon include benzene and toluene. Examples of the aliphatic hydrocarbon include aliphatic hydrocarbons having 5 to 7 carbon atoms, among which n-hexane is preferable. The mixing ratio (volume ratio) of the aromatic hydrocarbon and the aliphatic hydrocarbon is, for example, 1: 1 to 10, and preferably 4: 6.
　前記製造方法において、前記式（ＩＩ）で表される化合物は、市販で入手してもよいし、公知文献を参照して自家製造してもよい。式（ＩＩ）で表される化合物は、例えば、以下のようにして製造することができる。 In the production method, the compound represented by the formula (II) may be obtained commercially, or may be made in-house with reference to known literature. The compound represented by the formula (II) can be produced, for example, as follows.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　前記式中、ｎおよびＲは、式（Ｉ）における定義と同様である。 In the above formula, n and R are as defined in formula (I).
　式（ＩＩＩ）のサリチルアルデヒド誘導体と１当量のアミン（式（ＩＶ）の化合物）を、溶媒中で加熱することにより、式（ＩＩ）の化合物を得る。この反応は、例えば２０～１００℃で必要な時間、行う。この反応の溶媒としては、限定されないが、例えば、メタノール、ジメチルホルムアミド（ＤＭＦ）とメタノールの混合物、ジメチルスルホキシド（ＤＭＳＯ）等が挙げられる。 A compound of formula (II) is obtained by heating a salicylaldehyde derivative of formula (III) and 1 equivalent of an amine (compound of formula (IV)) in a solvent. This reaction is carried out, for example, at 20 to 100 ° C. for the necessary time. Examples of the solvent for this reaction include, but are not limited to, methanol, a mixture of dimethylformamide (DMF) and methanol, dimethyl sulfoxide (DMSO), and the like.
　本発明の式（Ｘ）で表される白金錯体は、式（Ｉ）で表される白金錯体と同様にして製造することができる。 The platinum complex represented by the formula (X) of the present invention can be produced in the same manner as the platinum complex represented by the formula (I).
　本発明の発光材料は、有機ＥＬ素子の発光材料、具体的には発光層の材料として用いることができる。そのような有機ＥＬ素子としては、例えば、基板、陽極、正孔輸送層、本発明の発光材料を含む発光層、電子輸送層、および陰極をこの順に積層して構成される。前記基板、陽極、正孔輸送層、電子輸送層、および陰極については、従来公知の材料を用い、従来公知の製造方法により形成されていてもよい。 The light emitting material of the present invention can be used as a light emitting material of an organic EL element, specifically, a material of a light emitting layer. As such an organic EL element, for example, a substrate, an anode, a hole transport layer, a light emitting layer containing the light emitting material of the present invention, an electron transport layer, and a cathode are laminated in this order. The substrate, the anode, the hole transport layer, the electron transport layer, and the cathode may be formed by a conventionally known manufacturing method using a conventionally known material.
　前記発光層は、本発明の発光材料のほかに、ホスト材料を含んでいてもよい。このホスト材料としては、例えば、ジアリールアミン骨格を有するもの、ピリジン骨格を有するもの、ピラジン骨格を有するもの、トリアジン骨格を有するもの、アリールシラン骨格を有するものが挙げられる。 The light emitting layer may contain a host material in addition to the light emitting material of the present invention. Examples of the host material include those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an arylsilane skeleton.
　以下に本発明を実施例によりさらに具体的に説明するが、本発明の範囲は、以下の実施例により限定されない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the following examples.
　種々のスペクトルは、以下の機器を用いて測定した。
　核磁気共鳴（ＮＭＲ）スペクトルはバリアン社製ＵＮＩＴＹ－ＩＮＯＶＡ核磁気共鳴装置（５００ＭＨｚ）を用いて測定し、測定溶媒の残存シグナルを内部基準として使用した。 Various spectra were measured using the following instrument.
The nuclear magnetic resonance (NMR) spectrum was measured using a UNITY-INOVA nuclear magnetic resonance apparatus (500 MHz) manufactured by Varian, and the residual signal of the measurement solvent was used as an internal reference.
　量子収率は、蛍光光度計ＦＰ－６５００Ｎ、燐光測定対応低温中積分球システムＩＮＫ－５３３、および、液体試料用セルＬＰＨ－１２０（全て日本分光株式会社製）を用いて測定した。 The quantum yield was measured using a fluorometer FP-6500N, a low-temperature medium integrating sphere system INK-533 for phosphorescence measurement, and a liquid sample cell LPH-120 (all manufactured by JASCO Corporation).
　本明細書の記載において、以下の略語を使用する。
　ＤＭＳＯ：ジメチルスルホキシド The following abbreviations are used in the description of the present specification.
DMSO: Dimethyl sulfoxide
　［実施例１］
　trans-ビス（N-オクチルサリチルアルジミナト）白金(II)(１)の合成 [Example 1]
Synthesis of trans-bis (N-octylsalicylaldiminato) platinum (II) (1)
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　化合物（１）をスキーム１に従い、合成した。サリチルアルデヒド（ＩＩＩ－１）と１当量のオクチルアミン（ＩＶ－１）をエタノール中で加熱還流することで合成したＮ－オクチルサリチルアルジミン配位子（ＩＩ－１）（３６２ｍｇ）と、ＰｔＣｌ2（ＣＨ3ＣＮ）2（２８６ｍｇ）、Ｋ2ＣＯ3（６９２ｍｇ）をＤＭＳＯ（４．５ｍＬ）中、１１０℃で２０時間反応させた。室温まで冷却したのち、水（９ｍＬ）を加え、生じた固体を吸引ろ過で集めた。ＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（１）を得た（オレンジ色粉末、１０９ｍｇ）。 Compound (1) was synthesized according to Scheme 1. N-octylsalicylaldimine ligand (II-1) (362 mg) synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of octylamine (IV-1) in ethanol, PtCl 2 ( CH 3 CN) 2 (286 mg) and K 2 CO 3 (692 mg) were reacted in DMSO (4.5 mL) at 110 ° C. for 20 hours. After cooling to room temperature, water (9 mL) was added and the resulting solid was collected by suction filtration. Compound (1) was obtained by purification with NH-silica gel column chromatography (eluent: CH 2 Cl 2 ) (orange powder, 109 mg).
　1H NMR (500 MHz, CDCl3) δ 0.87 (t, J = 6.9 Hz, 6 H), 1.20-1.45 (m, 20H), 1.82 (quin, J = 7.4 Hz, 4 H), 3.84 (t, J = 7.4 Hz, 4 H), 6.59 (t, J = 7.3 Hz, 2 H), 6.88 (d, J = 8.5 Hz, 2 H), 7.25 (dd, J = 7.5, 1.6 Hz, 2 H), 7.33 (td, J = 7.6, 1.8 Hz, 2 H), 7.91 (s, 2 H);
HRMS (FAB+) m/z [M+H]+ C30H45O2N2 194Ptについて計算値: 659.3108, 測定値: 659.3088。 1 H NMR (500 MHz, CDCl 3 ) δ 0.87 (t, J = 6.9 Hz, 6 H), 1.20-1.45 (m, 20H), 1.82 (quin, J = 7.4 Hz, 4 H), 3.84 (t, J = 7.4 Hz, 4 H), 6.59 (t, J = 7.3 Hz, 2 H), 6.88 (d, J = 8.5 Hz, 2 H), 7.25 (dd, J = 7.5, 1.6 Hz, 2 H), 7.33 (td, J = 7.6, 1.8 Hz, 2 H), 7.91 (s, 2 H);
HRMS (FAB + ) m / z [M + H] + Calculated for C 30 H 45 O 2 N 2 194 Pt: 659.3108, found: 659.3088.
　［実施例２］
　trans-ビス（N-ヘキサデシルサリチルアルジミナト）白金(II)(２)の合成 [Example 2]
Synthesis of trans-bis (N-hexadecylsalicylaldiminato) platinum (II) (2)
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　化合物（２）をスキーム２に従い、合成した。サリチルアルデヒド(ＩＩＩ-１)と１当量のヘキサデシルアミン(ＩＶ-２)をエタノール中で加熱還流することで合成したＮ－ヘキサデシルサリチルアルジミン配位子(ＩＩ-２)（６９１ｍｇ）と、ＰｔＣｌ2（ＣＨ3ＣＮ）2（３４８ｍｇ）、Ｋ2ＣＯ3（９０１ｍｇ）をＤＭＳＯ（６ｍＬ）中、１１０℃で２０時間反応させた。室温まで冷却したのち、水（１２ｍＬ）を加え、生じた固体を吸引ろ過で集めた。ＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（２）を得た（オレンジ色粉末、４４６ｍｇ）。 Compound (2) was synthesized according to Scheme 2. N-hexadecylsalicylaldimine ligand (II-2) (691 mg) synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of hexadecylamine (IV-2) in ethanol, PtCl 2 (CH 3 CN) 2 (348 mg) and K 2 CO 3 (901 mg) were reacted in DMSO (6 mL) at 110 ° C. for 20 hours. After cooling to room temperature, water (12 mL) was added and the resulting solid was collected by suction filtration. Purification by NH-silica gel column chromatography (eluent; CH 2 Cl 2 ) gave compound (2) (orange powder, 446 mg).
　1H NMR (500 MHz, CDCl3) δ 0.88 (t, J = 7.1 Hz, 6 H), 1.19-1.44 (m, 52 H), 1.82 (quin, J = 7.4 Hz, 4 H), 3.84 (t, J = 7.5 Hz, 4 H), 6.59 (t, J = 7.8 Hz, 2 H), 6.88 (d, J = 8.0 Hz, 2 H), 7.25 (dd, J = 8.0, 1.8 Hz, 2 H), 7.33 (td, J = 7.6, 1.8 Hz, 2 H), 7.91 (s, 2 H);
HRMS (FAB+) m/z [M]+ C46H76O2N2 195Ptについて計算値:883.5552, 測定値: 883.5569. 1 H NMR (500 MHz, CDCl 3 ) δ 0.88 (t, J = 7.1 Hz, 6 H), 1.19-1.44 (m, 52 H), 1.82 (quin, J = 7.4 Hz, 4 H), 3.84 (t , J = 7.5 Hz, 4 H), 6.59 (t, J = 7.8 Hz, 2 H), 6.88 (d, J = 8.0 Hz, 2 H), 7.25 (dd, J = 8.0, 1.8 Hz, 2 H) , 7.33 (td, J = 7.6, 1.8 Hz, 2 H), 7.91 (s, 2 H);
HRMS (FAB + ) m / z [M] + C 46 H 76 O 2 N 2 For 195 Pt: Calculated: 883.5552, Measurement: 883.5569.
　［実施例３］
　trans-ビス（N-オクタデシルサリチルアルジミナト）白金(II)(３)の合成 [Example 3]
Synthesis of trans-bis (N-octadecylsalicylaldiminato) platinum (II) (3)
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　化合物（３）をスキーム３に従い、合成した。サリチルアルデヒド(ＩＩＩ-１)と１当量のオクタデシルアミン(ＩＶ-３)をエタノール中で加熱還流することで合成したＮ－オクタデシルサリチルアルジミン配位子(ＩＩ-３)（３７３ｍｇ）と、ＰｔＣｌ2（ＣＨ3ＣＮ）2（１７５ｍｇ）、Ｋ2ＣＯ3（４５９ｍｇ）をＤＭＳＯ（３ｍＬ）中、１１０℃で２０時間反応させた。室温まで冷却したのち、水（６ｍＬ）を加え、生じた固体を吸引ろ過で集めた。ＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（３）を得た（オレンジ色粉末、２１２ｍｇ）。 Compound (3) was synthesized according to Scheme 3. N-octadecylsalicylaldimine ligand (II-3) (373 mg) synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of octadecylamine (IV-3) in ethanol, PtCl 2 ( CH 3 CN) 2 (175 mg) and K 2 CO 3 (459 mg) were reacted in DMSO (3 mL) at 110 ° C. for 20 hours. After cooling to room temperature, water (6 mL) was added and the resulting solid was collected by suction filtration. Purification by NH-silica gel column chromatography (eluent; CH 2 Cl 2 ) gave compound (3) (orange powder, 212 mg).
　1H NMR (500 MHz, CDCl3) δ 0.88 (t, J = 7.0 Hz, 6 H), 1.17-1.44 (m, 60 H), 1.82 (quin, J = 7.5 Hz, 4 H), 3.84 (t, J = 7.4 Hz, 4 H), 6.59 (td, J = 7.4, 1.1 Hz, 2 H), 6.88 (d, J = 8.5 Hz, 2 H), 7.25 (dd, J = 7.8, 1.8 Hz, 2 H), 7.33 (td, J = 7.8, 1.8 Hz, 2 H), 7.91 (s, 2 H);
HRMS (FAB+) m/z [M]+ C50H84O2N2 196Ptについて計算値: 940.6182, 測定値: 940.6167。 1 H NMR (500 MHz, CDCl 3 ) δ 0.88 (t, J = 7.0 Hz, 6 H), 1.17-1.44 (m, 60 H), 1.82 (quin, J = 7.5 Hz, 4 H), 3.84 (t , J = 7.4 Hz, 4 H), 6.59 (td, J = 7.4, 1.1 Hz, 2 H), 6.88 (d, J = 8.5 Hz, 2 H), 7.25 (dd, J = 7.8, 1.8 Hz, 2 H), 7.33 (td, J = 7.8, 1.8 Hz, 2 H), 7.91 (s, 2 H);
HRMS (FAB + ) m / z [M] + calculated for C 50 H 84 O 2 N 2 196 Pt: 940.6182, found: 940.6167.
　［実施例４］
　trans-ビス（N-ヘキサデシル-４-メトキシサリチルアルジミナト）白金(II)(４)の合成 [Example 4]
Synthesis of trans-bis (N-hexadecyl-4-methoxysalicylaldiminato) platinum (II) (4)
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　化合物（４）をスキーム４に従い合成した。４－メトキシサリチルアルデヒド(ＩＩＩ-２)と1等量のヘキサデシルアミン(ＩＶ-２)をエタノール中で加熱還流することにより合成したＮ－ヘキサデシル-４-メトキシサチリルアルジミン配位子（ＩＩ－４）(５６４ｍｇ)と、ＰｔＣｌ2（ＣＨ3ＣＮ）2（２６２ｍｇ）、Ｋ2ＣＯ3（６８８ｍｇ）をＤＭＳＯ（４．５ｍＬ）中、１１０℃で２０時間反応させた。室温まで冷却したのち、水（９ｍＬ）を加え、生じた固体を吸引ろ過で集めた。ＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（４）を得た（オレンジ色粉末、４１８ｍｇ）。 Compound (4) was synthesized according to Scheme 4. N-hexadecyl-4-methoxysatilylaldimine ligand (II-) synthesized by heating and refluxing 4-methoxysalicylaldehyde (III-2) and 1 equivalent of hexadecylamine (IV-2) in ethanol 4) (564 mg), PtCl 2 (CH 3 CN) 2 (262 mg), and K 2 CO 3 (688 mg) were reacted in DMSO (4.5 mL) at 110 ° C. for 20 hours. After cooling to room temperature, water (9 mL) was added and the resulting solid was collected by suction filtration. Compound (4) was obtained by purification with NH-silica gel column chromatography (eluent; CH 2 Cl 2 ) (orange powder, 418 mg).
　1H NMR (500 MHz, CDCl3) δ 0.88 (t, J = 6.7 Hz, 6 H), 1.14-1.45 (m, 52 H), 1.81 (quin, J = 6.9 Hz, 4 H), 3.72-3.82 (m, 4 H), 3.77 (s, 6 H), 6.23 (dd, J = 8.7, 2.4 Hz, 2 H), 6.33 (d, J = 2.4 Hz, 2 H), 7.12 (d, J = 8.7 Hz, 2 H), 7.76 (s, 2 H); 
HRMS (FAB+) m/z [M]+ C48H80O4N2 195Ptについて計算値:943.5766, 測定値: 943.5730。 1 H NMR (500 MHz, CDCl 3 ) δ 0.88 (t, J = 6.7 Hz, 6 H), 1.14-1.45 (m, 52 H), 1.81 (quin, J = 6.9 Hz, 4 H), 3.72-3.82 (m, 4 H), 3.77 (s, 6 H), 6.23 (dd, J = 8.7, 2.4 Hz, 2 H), 6.33 (d, J = 2.4 Hz, 2 H), 7.12 (d, J = 8.7 Hz, 2 H), 7.76 (s, 2 H);
HRMS (FAB +) m / z [M] + C 48 H 80 O 4 N 2 195 Pt for Calculated: 943.5766, Found: 943.5730.
　［実施例５］
　trans-ビス（N-ドデシルサリチルアルジミナト）白金(II)(５)の合成 [Example 5]
Synthesis of trans-bis (N-dodecylsalicylaldiminato) platinum (II) (5)
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　化合物（５）をスキーム５に従い、合成した。サリチルアルデヒド（ＩＩＩ－１）と１当量のドデシルアミン（ＩＶ－４）をエタノール中で加熱還流することで合成したＮ－ドデシルサリチルアルジミン配位子（ＩＩ－５）（２９３ｍｇ）と、ＰｔＣｌ2（ＣＨ3ＣＮ）2（１７６ｍｇ）、Ｋ2ＣＯ3（４５９ｍｇ）をＤＭＳＯ（３ｍＬ）中、１１０℃で２０時間反応させた。室温まで冷却したのち、水（６ｍＬ）を加え、生じた固体を吸引ろ過で集めた。ＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（５）を得た（オレンジ色粉末、１４２ｍｇ）。 Compound (5) was synthesized according to Scheme 5. N-dodecylsalicylaldimine ligand (II-5) (293 mg) synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of dodecylamine (IV-4) in ethanol, PtCl 2 ( CH 3 CN) 2 (176 mg) and K 2 CO 3 (459 mg) were reacted in DMSO (3 mL) at 110 ° C. for 20 hours. After cooling to room temperature, water (6 mL) was added and the resulting solid was collected by suction filtration. Purification by NH-silica gel column chromatography (eluent; CH 2 Cl 2 ) gave compound (5) (orange powder, 142 mg).
　1H NMR (500 MHz, CDCl3) δ 0.88 (t, J = 7.1 Hz, 6 H), 1.20-1.43 (m, 36H), 1.82 (quin, J = 7.0 Hz, 4 H), 3.84 (t, J = 7.5 Hz, 4 H), 6.59 (td, J = 7.5, 1.3 Hz, 2 H), 6.88 (d, J = 8.4 Hz, 2 H), 7.26 (dd, J = 8.0, 1.7 Hz, 2 H), 7.33 (td, J = 7.7, 1.7 Hz, 2 H), 7.91 (s, 2 H); 
HRMS (FAB+) m/z [M]+ C38H60O2N2 195Ptについて計算値: 771.4303, 測定値: 771.4321. 1 H NMR (500 MHz, CDCl 3 ) δ 0.88 (t, J = 7.1 Hz, 6 H), 1.20-1.43 (m, 36H), 1.82 (quin, J = 7.0 Hz, 4 H), 3.84 (t, J = 7.5 Hz, 4 H), 6.59 (td, J = 7.5, 1.3 Hz, 2 H), 6.88 (d, J = 8.4 Hz, 2 H), 7.26 (dd, J = 8.0, 1.7 Hz, 2 H ), 7.33 (td, J = 7.7, 1.7 Hz, 2 H), 7.91 (s, 2 H);
HRMS (FAB + ) m / z [M] + C 38 H 60 O 2 N 2 For 195 Pt Calculated: 771.4303, Measured: 771.4321.
　［比較例１］
　trans-ビス（N-メチルサリチルアルジミナト）白金(II)(１１)の合成 [Comparative Example 1]
Synthesis of trans-bis (N-methylsalicylaldiminato) platinum (II) (11)
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　化合物（１１）をスキーム６に従い、合成した。サリチルアルデヒド（ＩＩＩ－１）と１当量のメチルアミン（ＩＶ－６）をメタノール中で加熱還流することで合成したＮ－メチルサリチルアルジミン配位子（ＩＩ－７）（５４０ｍｇ）と、ＰｔＣｌ2（ＣＨ3ＣＮ）2（６９８ｍｇ）、Ｋ2ＣＯ3（１．８６ｇ）をＤＭＳＯ（１０ｍＬ）中、１１０℃で２０時間反応させた。室温まで冷却したのち、水（２０ｍＬ）を加え、生じた固体を吸引ろ過で集めた。ＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製後、酢酸エチルから再結晶することで、化合物（１１）を得た（オレンジ色粉末、１５８ｍｇ）。 Compound (11) was synthesized according to Scheme 6. N-methylsalicylaldimine ligand (II-7) (540 mg) synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of methylamine (IV-6) in methanol, PtCl 2 ( CH 3 CN) 2 (698 mg) and K 2 CO 3 (1.86 g) were reacted in DMSO (10 mL) at 110 ° C. for 20 hours. After cooling to room temperature, water (20 mL) was added and the resulting solid was collected by suction filtration. After purification by NH-silica gel column chromatography (eluent: CH 2 Cl 2 ), recrystallization from ethyl acetate gave Compound (11) (orange powder, 158 mg).
　1H NMR (500 MHz, CDCl3) δ 3.64 (s, 6 H), 6.59 (td, J = 7.4, 1.4 Hz, 2 H), 6.96 (d, J = 8.4 Hz, 2 H), 7.24 (dd, J = 8.0, 1.7 Hz, 2 H), 7.34 (td, J = 7.8, 1.7 Hz, 2 H), 7.91 (1 H, s);
元素分析：C16H16O2N2Ptについて計算値: C, 41.47; H, 3.48; N, 6.05. 測定値 C, 41.44; H, 3.38; N, 6.03。 1 H NMR (500 MHz, CDCl 3 ) δ 3.64 (s, 6 H), 6.59 (td, J = 7.4, 1.4 Hz, 2 H), 6.96 (d, J = 8.4 Hz, 2 H), 7.24 (dd , J = 8.0, 1.7 Hz, 2 H), 7.34 (td, J = 7.8, 1.7 Hz, 2 H), 7.91 (1 H, s);
Elemental analysis: Calculated for C 16 H 16 O 2 N 2 Pt: C, 41.47; H, 3.48; N, 6.05. Found C, 41.44; H, 3.38; N, 6.03.
　［比較例２］
　trans-ビス（N-ペンチルサリチルアルジミナト）白金 (II)(１２)の合成 [Comparative Example 2]
Synthesis of trans-bis (N-pentylsalicylaldiminato) platinum (II) (12)
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　化合物（１２）をスキーム７に従い、合成した。サリチルアルデヒド（ＩＩＩ－１）と１当量のペンチルアミン（ＩＶ－７）をエタノール中で加熱還流することで合成したＮ－ペンチルサリチルアルジミン配位子（ＩＩ－８）（１９１ｍｇ）と、ＰｔＣｌ2（ＣＨ3ＣＮ）2（１７４ｍｇ）、Ｋ2ＣＯ3（４６３ｍｇ）をＤＭＳＯ（３ｍＬ）中、１１０℃で２０時間反応させた。室温まで冷却したのち、水（９ｍＬ）を加え、生じた固体を吸引ろ過で集めた。ＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（１２）を得た（オレンジ色粉末、７７ｍｇ）。 Compound (12) was synthesized according to Scheme 7. N-pentylsalicylaldimine ligand (II-8) (191 mg) synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of pentylamine (IV-7) in ethanol, PtCl 2 ( CH 3 CN) 2 (174 mg) and K 2 CO 3 (463 mg) were reacted in DMSO (3 mL) at 110 ° C. for 20 hours. After cooling to room temperature, water (9 mL) was added and the resulting solid was collected by suction filtration. Purification by NH-silica gel column chromatography (eluent; CH 2 Cl 2 ) gave compound (12) (orange powder, 77 mg).
　1H NMR (500 MHz, CDCl3) δ 0.87 (t, J = 6.9 Hz, 6 H), 1.20-1.45 (m, 20H), 1.82 (quin, J = 7.4 Hz, 4 H), 3.84 (t, J = 7.4 Hz, 4 H), 6.59 (t, J = 7.3 Hz, 2 H), 6.88 (d, J = 8.5 Hz, 2 H), 7.25 (dd, J = 7.5, 1.6 Hz, 2 H), 7.33 (td, J = 7.6, 1.8 Hz, 2 H), 7.91 (s, 2 H); 
HRMS (FAB+) m/z [M+H]+ C30H45O2N2 194Ptについて計算値: 659.3108, 測定値: 659.3088。 1 H NMR (500 MHz, CDCl 3 ) δ 0.87 (t, J = 6.9 Hz, 6 H), 1.20-1.45 (m, 20H), 1.82 (quin, J = 7.4 Hz, 4 H), 3.84 (t, J = 7.4 Hz, 4 H), 6.59 (t, J = 7.3 Hz, 2 H), 6.88 (d, J = 8.5 Hz, 2 H), 7.25 (dd, J = 7.5, 1.6 Hz, 2 H), 7.33 (td, J = 7.6, 1.8 Hz, 2 H), 7.91 (s, 2 H);
HRMS (FAB + ) m / z [M + H] + Calculated for C 30 H 45 O 2 N 2 194 Pt: 659.3108, found: 659.3088.
　［固体発光量子収率の測定］
　実施例１～５および比較例１～２で得た化合物（１）～（５）および（１１）～（１２）について、２９６Ｋおよび７７Ｋにおける固体発光量子収率φ（％）を測定した。具体的には、化合物（１）～（５）および（１１）～（１２）の結晶状態（粉末）における発光量子収率を、絶対法によりそれぞれ求めた。化合物（１）～（５）は、加熱して調製したｎ－ヘキサン／ベンゼン（体積比は、ｎ－ヘキセン／ベンゼン＝６／４）の溶液を室温で放冷することにより結晶化した結晶を用いた。化合物（１１）および（１２）は、加熱して調製した酢酸エチルの溶液を室温で放冷することにより結晶化した結晶を用いた。測定方法は以下の通りである。 [Measurement of solid-state luminescence quantum yield]
With respect to the compounds (1) to (5) and (11) to (12) obtained in Examples 1 to 5 and Comparative Examples 1 to 2, the solid-state emission quantum yield φ (%) at 296K and 77K was measured. Specifically, the emission quantum yields of the compounds (1) to (5) and (11) to (12) in the crystalline state (powder) were determined by the absolute method. Compounds (1) to (5) are crystals obtained by heating a solution of n-hexane / benzene (volume ratio: n-hexene / benzene = 6/4) prepared by heating at room temperature. Using. As the compounds (11) and (12), crystals crystallized by heating a solution of ethyl acetate prepared by heating at room temperature were used. The measuring method is as follows.
　（測定方法）
　測定の際、酸素の影響を除くため、全てのサンプルは、石英セル中に結晶（化合物（１）～（５）および（１１）～（１２））をそのまま封入して、アルゴン雰囲気下で測定した。さらに、低温（７７Ｋ）での測定は、石英製デュワーを用いて、結晶を封入した上記石英セルを液体窒素で冷やしながら測定した。全ての発光スペクトルは、標準光源を利用することにより補正を行った。励起光として４２０ｎｍの波長の光を用いた。内部量子収率の算出には、固体量子効率計算プログラム（日本分光株式会社製）を用いた。また、各有機白金錯体が発する光の発光極大波長も、併せて測定した。測定結果を表１に示す。 (Measuring method)
In order to eliminate the influence of oxygen during measurement, all samples were measured in an argon atmosphere with crystals (compounds (1) to (5) and (11) to (12)) enclosed in a quartz cell. did. Furthermore, the measurement at low temperature (77K) was performed using a quartz dewar while cooling the quartz cell in which the crystal was sealed with liquid nitrogen. All emission spectra were corrected by using a standard light source. Light having a wavelength of 420 nm was used as excitation light. For the calculation of the internal quantum yield, a solid quantum efficiency calculation program (manufactured by JASCO Corporation) was used. Moreover, the light emission maximum wavelength of the light emitted from each organic platinum complex was also measured. The measurement results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
　前記表１に示すように、実施例１～５および比較例１～２の結果から、式（Ｉ）で表される白金錯体は、結晶状態において、室温において高い量子効率で燐光発光を示すことが確認できた。 As shown in Table 1, the results of Examples 1 to 5 and Comparative Examples 1 and 2 indicate that the platinum complex represented by the formula (I) exhibits phosphorescence with high quantum efficiency at room temperature in the crystalline state. Was confirmed.
　［粉末Ｘ線回折］
　実施例１の化合物（１）、実施例２の化合物（２）、実施例３の化合物（３）、実施例４の化合物（４）および、実施例５の化合物（５）ならびに比較例１の化合物（１１）および比較例２の化合物（１２）について、フィリップス（Philips）社製Ｘ’Ｐｅｒｔ－ＭＰＤ粉末Ｘ線回折測定装置を用いて粉末Ｘ線回折を測定した。Ｘ線は、Ｃｕ－Ｋα線（λ＝１．５４０６Å）を用いた。実施例１の化合物（１）、実施例２の化合物（２）、実施例３の化合物（３）、実施例４の化合物（４）および、実施例５の化合物（５）は、加熱して調製したｎ－ヘキサン／ベンゼン（体積比は、ｎ－ヘキセン／ベンゼン＝６／４）の溶液を室温で放冷することにより結晶化した結晶を用いた。得られた実施例１の化合物（１）のＸＲＤパターンを図１に、実施例２の化合物（２）のＸＲＤパターンを図２に、実施例３の化合物（３）のＸＲＤパターンを図３に、実施例４の化合物（４）のＸＲＤパターンを図４に、実施例５の化合物（５）のＸＲＤパターンを図５に、比較例１の化合物（１１）の単結晶Ｘ線構造解析結果からシミュレーションにより求めたＸＲＤパターンを図６に、比較例２の化合物（１２）の単結晶Ｘ線構造解析結果からシミュレーションにより求めたＸＲＤパターンを図７に示す。 [Powder X-ray diffraction]
Example 1 Compound (1), Example 2 Compound (2), Example 3 Compound (3), Example 4 Compound (4), Example 5 Compound (5) and Comparative Example 1 The compound (11) and the compound (12) of Comparative Example 2 were measured for powder X-ray diffraction using an X′Pert-MPD powder X-ray diffractometer manufactured by Philips. As the X-ray, Cu—Kα ray (λ = 1.5406 mm) was used. The compound (1) of Example 1, the compound (2) of Example 2, the compound (3) of Example 3, the compound (4) of Example 4 and the compound (5) of Example 5 were heated. Crystals crystallized by allowing the prepared n-hexane / benzene (volume ratio: n-hexene / benzene = 6/4) solution to cool at room temperature were used. The XRD pattern of the obtained compound (1) of Example 1 is shown in FIG. 1, the XRD pattern of the compound (2) of Example 2 is shown in FIG. 2, and the XRD pattern of the compound (3) of Example 3 is shown in FIG. The XRD pattern of the compound (4) of Example 4 is shown in FIG. 4, the XRD pattern of the compound (5) of Example 5 is shown in FIG. 5, and the single crystal X-ray structural analysis result of the compound (11) of Comparative Example 1 is shown in FIG. FIG. 6 shows an XRD pattern obtained by simulation, and FIG. 7 shows an XRD pattern obtained by simulation from the single crystal X-ray structural analysis result of the compound (12) of Comparative Example 2.
　［単結晶Ｘ線構造解析］
　実施例２の化合物（２）ならびに比較例１の化合物（１１）および比較例２の化合物（１２）について、株式会社リガク社製イメージングプレート単結晶自動Ｘ線構造解析装置ＰＡＰＩＤ－ＡＵＴＯを用いて単結晶Ｘ線結晶解析を行った。Ｘ線は、Ｍｏ－Ｋa線（λ＝０．７１０７５Å）を用いた。実施例２の化合物（２）は、加熱して調製したｎ－ヘキサン／ベンゼン（体積比は、ｎ－ヘキセン／ベンゼン＝６／４）の溶液を室温で放冷することにより結晶化した結晶を用いた。得られた結晶解析の結果得られた実施例２の化合物（２）の結晶中におけるパッキング図を図８に、比較例１の化合物（１１）の結晶中におけるパッキング図を図９に、比較例２の化合物（１２）の結晶中におけるパッキング図を図１０に示す。 [Single-crystal X-ray structure analysis]
About the compound (2) of Example 2, the compound (11) of Comparative Example 1 and the compound (12) of Comparative Example 2, the imaging plate single crystal automatic X-ray structure analyzer PAAPID-AUTO manufactured by Rigaku Co., Ltd. Crystal X-ray crystal analysis was performed. As the X-ray, a Mo—Ka ray (λ = 0.71075 mm) was used. Compound (2) of Example 2 was obtained by cooling a solution of n-hexane / benzene (volume ratio: n-hexene / benzene = 6/4) prepared by heating at room temperature. Using. FIG. 8 shows a packing diagram in the crystal of the compound (2) of Example 2 obtained as a result of the obtained crystal analysis, FIG. 9 shows a packing diagram in the crystal of the compound (11) of Comparative Example 1, and FIG. FIG. 10 shows a packing diagram of the compound (12) of 2 in the crystal.
　図１～図５に示すように、実施例の白金錯体は、結晶中において分子が層状に並び、かつ、ｎの数（アルキル鎖の長さ）に応じた格子面間隔（ｄ）を有するラメラ構造をとることが確認できた。一方、図６および図７に示すように、比較例の白金錯体においては、このようなラメラ構造はとらないことが確認できた。 As shown in FIGS. 1 to 5, the platinum complex of the example has a lamellar structure in which molecules are arranged in layers in a crystal and have a lattice spacing (d) corresponding to the number of n (length of alkyl chain). It was confirmed that the structure was adopted. On the other hand, as shown in FIGS. 6 and 7, it was confirmed that the platinum complex of the comparative example did not have such a lamellar structure.
　また、図８に示すように、実施例２の化合物（２）は、層状構造を有し、その層の周期は、前記ＸＲＤスペクトルの面間隔（ｄ＝２６．７Å）に対応することが確認できた。一方、図９および図１０に示すように、比較例の白金錯体は、層状構造を有さないことが確認できた。 Further, as shown in FIG. 8, it is confirmed that the compound (2) of Example 2 has a layered structure, and the period of the layer corresponds to the interplanar spacing (d = 26.7Å) of the XRD spectrum. did it. On the other hand, as shown in FIGS. 9 and 10, it was confirmed that the platinum complex of the comparative example did not have a layered structure.
　このように、式（Ｉ）で表される化合物は、結晶中における分子の配列がラメラ構造をとる。その結果、式（Ｉ）で表される化合物は結晶状態で分子間で消光しあわないため、強い強度の燐光発光が実現できると考えられる。 Thus, in the compound represented by the formula (I), the molecular arrangement in the crystal has a lamellar structure. As a result, since the compound represented by the formula (I) does not quench between molecules in a crystalline state, it is considered that strong intensity phosphorescence can be realized.
　本発明の発光材料は、固体であって、かつ、発光効率に優れるため、実用に足る発光強度を得ることができる。従って、本発明の発光材料は、次世代技術である有機発光素子等の材料として有用である。 Since the light emitting material of the present invention is solid and has excellent light emission efficiency, it is possible to obtain light emission intensity sufficient for practical use. Therefore, the light-emitting material of the present invention is useful as a material for organic light-emitting elements that are the next generation technology.

Claims (8)

  1. 　式（Ｉ）で表される白金錯体を含む発光材料。
    Figure JPOXMLDOC01-appb-C000001
     ［前記式中、ｎは、７～２５の整数であり、かつＲは、水素原子または炭素数１～６を有するアルコキシ基である。］     A light emitting material containing a platinum complex represented by the formula (I).
    Figure JPOXMLDOC01-appb-C000001
     [In the above formula, n is an integer of 7 to 25, and R is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms. ]
  2. 　ｎが８～１８の整数であり、かつＲは水素原子または炭素数１～３を有するアルコキシ基である請求項１に記載の発光材料。 2. The luminescent material according to claim 1, wherein n is an integer of 8 to 18, and R is a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms.
  3. 　式（Ｘ）で表される白金錯体。
    Figure JPOXMLDOC01-appb-C000002
     ［前記式中、ｍは、７～１１または１３～２５の整数であり、かつＲ’は、水素原子または炭素数１～６を有するアルコキシ基であるか、または、
    ｍは、１２であり、かつＲ’は、炭素数１～６を有するアルコキシ基である。］     A platinum complex represented by the formula (X).
    Figure JPOXMLDOC01-appb-C000002
     [Wherein, m is an integer of 7 to 11 or 13 to 25, and R ′ is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, or
    m is 12 and R ′ is an alkoxy group having 1 to 6 carbon atoms. ]
  4. 　ｍが７～１１または１３～１９の整数であり、かつ、Ｒ’が水素原子である請求項３に記載の白金錯体。 The platinum complex according to claim 3, wherein m is an integer of 7 to 11 or 13 to 19, and R 'is a hydrogen atom.
  5. 　ｍが７～１９の整数であり、かつ、Ｒ’が炭素数１～６を有するアルコキシ基である請求項３に記載の白金錯体。 4. The platinum complex according to claim 3, wherein m is an integer of 7 to 19 and R ′ is an alkoxy group having 1 to 6 carbon atoms.
  6. 　式（１）～式（４）のいずれかで表される請求項３に記載の白金錯体。
    Figure JPOXMLDOC01-appb-C000003
         The platinum complex according to claim 3, which is represented by any one of formulas (1) to (4).
    Figure JPOXMLDOC01-appb-C000003
  7. 　単結晶Ｘ線構造解析において、式（Ｉ）で表される白金錯体が、ラメラ構造をとる請求項１または２に記載の発光材料。 The luminescent material according to claim 1 or 2, wherein the platinum complex represented by the formula (I) has a lamellar structure in single crystal X-ray structural analysis.
  8. 　式（Ｉ）で表される白金錯体が、芳香族炭化水素と脂肪族炭化水素との混合物から再結晶される請求項１または２に記載の発光材料。 The luminescent material according to claim 1 or 2, wherein the platinum complex represented by the formula (I) is recrystallized from a mixture of an aromatic hydrocarbon and an aliphatic hydrocarbon.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015053291A1 (en) * 2013-10-11 2015-04-16 国立大学法人大阪大学 Light-emitting material including platinum complex
CN105294489A (en) * 2015-10-18 2016-02-03 桂林理工大学 4-formyl benzoic adamantanol ester condensation bromoaniline Schiff base nickel complex synthesis and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003342278A (en) * 2002-05-30 2003-12-03 Ricoh Co Ltd Electric field light-generating zinc chelate, light- generating composition and organic electric field light- generating element
JP2011046699A (en) * 2009-07-31 2011-03-10 Sumitomo Chemical Co Ltd Metal complex, composition including the same, and light-emitting element using the same
WO2012121189A1 (en) * 2011-03-10 2012-09-13 国立大学法人九州大学 Phosphorescent material, process for producing phosphorescent material, and phosphorescent element
JP2012222255A (en) * 2011-04-12 2012-11-12 Fujifilm Corp Organic electroluminescent element, material and film for organic electroluminescent element, and manufacturing method for organic electroluminescent element

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003342278A (en) * 2002-05-30 2003-12-03 Ricoh Co Ltd Electric field light-generating zinc chelate, light- generating composition and organic electric field light- generating element
JP2011046699A (en) * 2009-07-31 2011-03-10 Sumitomo Chemical Co Ltd Metal complex, composition including the same, and light-emitting element using the same
WO2012121189A1 (en) * 2011-03-10 2012-09-13 国立大学法人九州大学 Phosphorescent material, process for producing phosphorescent material, and phosphorescent element
JP2012222255A (en) * 2011-04-12 2012-11-12 Fujifilm Corp Organic electroluminescent element, material and film for organic electroluminescent element, and manufacturing method for organic electroluminescent element

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015053291A1 (en) * 2013-10-11 2015-04-16 国立大学法人大阪大学 Light-emitting material including platinum complex
CN105294489A (en) * 2015-10-18 2016-02-03 桂林理工大学 4-formyl benzoic adamantanol ester condensation bromoaniline Schiff base nickel complex synthesis and application

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