JP4958263B2 - Organic light-emitting compound and light-emitting layer containing the compound - Google Patents
Organic light-emitting compound and light-emitting layer containing the compound Download PDFInfo
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- JP4958263B2 JP4958263B2 JP2006243886A JP2006243886A JP4958263B2 JP 4958263 B2 JP4958263 B2 JP 4958263B2 JP 2006243886 A JP2006243886 A JP 2006243886A JP 2006243886 A JP2006243886 A JP 2006243886A JP 4958263 B2 JP4958263 B2 JP 4958263B2
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- 150000001875 compounds Chemical class 0.000 title claims description 58
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- KLTWGRFNJPLFDA-UHFFFAOYSA-N benzimidazolide Chemical compound C1=CC=C2[N-]C=NC2=C1 KLTWGRFNJPLFDA-UHFFFAOYSA-N 0.000 description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 229910052786 argon Inorganic materials 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 230000005284 excitation Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 125000003118 aryl group Chemical group 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 125000005843 halogen group Chemical group 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 125000002252 acyl group Chemical group 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000002189 fluorescence spectrum Methods 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 235000002597 Solanum melongena Nutrition 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003480 eluent Substances 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical class N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006862 quantum yield reaction Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical group C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 3
- FZDQJVHCAWGPRW-UHFFFAOYSA-N 6-(5-ethoxycarbonylpyridin-2-yl)pyridine-3-carboxylic acid Chemical compound CCOC(=O)c1ccc(nc1)-c1ccc(cn1)C(O)=O FZDQJVHCAWGPRW-UHFFFAOYSA-N 0.000 description 3
- FCNCGHJSNVOIKE-UHFFFAOYSA-N 9,10-diphenylanthracene Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 FCNCGHJSNVOIKE-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RRXRZVYGVKJPRR-UHFFFAOYSA-N 2-n-hexylbenzene-1,2-diamine Chemical compound CCCCCCNC1=CC=CC=C1N RRXRZVYGVKJPRR-UHFFFAOYSA-N 0.000 description 2
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 2
- 238000002284 excitation--emission spectrum Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000990 laser dye Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- CAGNORWIUGYFLJ-UHFFFAOYSA-N n-hexyl-2-nitroaniline Chemical compound CCCCCCNC1=CC=CC=C1[N+]([O-])=O CAGNORWIUGYFLJ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- BOUOQESVDURNSB-UHFFFAOYSA-N 2-pyridin-3-yl-1h-benzimidazole Chemical compound N=1C2=CC=CC=C2NC=1C1=CC=CN=C1 BOUOQESVDURNSB-UHFFFAOYSA-N 0.000 description 1
- OFDVABAUFQJWEZ-UHFFFAOYSA-N 3-pyridin-3-ylpyridine Chemical group C1=CN=CC(C=2C=NC=CC=2)=C1 OFDVABAUFQJWEZ-UHFFFAOYSA-N 0.000 description 1
- PTRATZCAGVBFIQ-UHFFFAOYSA-N Abametapir Chemical compound N1=CC(C)=CC=C1C1=CC=C(C)C=N1 PTRATZCAGVBFIQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- BZDGCIJWPWHAOF-UHFFFAOYSA-N benzene-1,2,4,5-tetramine;hydron;tetrachloride Chemical compound Cl.Cl.Cl.Cl.NC1=CC(N)=C(N)C=C1N BZDGCIJWPWHAOF-UHFFFAOYSA-N 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YJBKVPRVZAQTPY-UHFFFAOYSA-J tetrachlorostannane;dihydrate Chemical compound O.O.Cl[Sn](Cl)(Cl)Cl YJBKVPRVZAQTPY-UHFFFAOYSA-J 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
本発明は、有機発光性化合物及びその化合物を含有する発光層に関する。より詳しくいえば、優れた光物性を有する、酸素の影響を受けない有機発光性化合物及びその化合物を含有する発光層に関する。 The present invention relates to an organic light emitting compound and a light emitting layer containing the compound. More specifically, the present invention relates to an organic light-emitting compound having excellent optical properties and not affected by oxygen, and a light-emitting layer containing the compound.
近年、光関連技術の進歩に伴い、有機エレクトロルミネセンス（有機ＥＬ）発光材料、レーザー色素、発光性試薬類など、新しい有機発光性化合物の開発が望まれている。
有機発光性化合物は、置換基を導入するなどして励起ならびに発光波長を変化させたり、被測定化合物などの認識機能の付加や高分子化など様々な高機能化が可能である。従って、発光性を示す新規な基本骨格構造の発見は多様な発展をもたらすことから、特に注目され多くの研究が行なわれている。
In recent years, development of new organic light-emitting compounds such as organic electroluminescence (organic EL) light-emitting materials, laser dyes, and light-emitting reagents has been desired with the progress of light-related technologies.
Organic light-emitting compounds can be enhanced in various functions, such as by introducing substituents to change excitation and emission wavelengths, adding recognition functions such as compounds to be measured, and increasing the molecular weight. Accordingly, the discovery of a novel basic skeletal structure exhibiting luminescent properties brings about various developments, and thus has attracted particular attention and many studies have been conducted.
有機発光性化合物の用途としては、例えば、細胞内蛍光プローブ、天然色画像の表現に必要な波長領域の光を出す有機ＥＬの発光体、色素レーザーの多様な波長に対応した色素等の多様な用途が挙げられる。特に、発光材料としての利用には、充分な発光量と、色の再現に適した、他の発光材料とのバランスの取れた組み合わせが可能なものが望まれる。また、蛍光材料としては、基本的には発光量子収率が高いことが望ましく、プローブ材料としては、励起光と蛍光との識別性が良く、生物学的な測定においては、励起波長が被測定材料を損傷させないものが望まれる。 Applications of organic light-emitting compounds include, for example, intracellular fluorescent probes, organic EL light emitters that emit light in the wavelength region necessary for the expression of natural color images, and dyes corresponding to various wavelengths of dye lasers. Applications are listed. In particular, for use as a light emitting material, a material capable of combining a sufficient amount of light emission and a balanced combination with other light emitting materials suitable for color reproduction is desired. In addition, as a fluorescent material, it is basically desirable that the emission quantum yield is high. As a probe material, the distinction between excitation light and fluorescence is good. In biological measurement, the excitation wavelength is measured. What does not damage the material is desired.
そこで、本発明者らは、発光材料の中でも、コンパクトディスク（ＣＤ）等への高密度記録に使用されるなど近年特に需要が高まっている青色発光性化合物に注目し、従来のジスチリルビフェニル系発光材、アリールエチニルベンゼン系発光材、セキシフェニル系発光材、ベンゾイミダゾール誘導体系発光材等の青色発光性化合物よりも合成が容易で、かつ高輝度、高効率の有機低分子青色発光材料の研究を行なってきた。 Accordingly, the present inventors have focused on blue light-emitting compounds that have been particularly demanding in recent years, such as being used for high-density recording on compact discs (CDs), among other light-emitting materials. Research on organic low-molecular blue light-emitting materials that are easier to synthesize and have higher brightness and higher efficiency than blue light-emitting compounds such as luminescent materials, arylethynylbenzene-based luminescent materials, sexiphenyl-based luminescent materials, and benzimidazole derivative-based luminescent materials I have done it.
特許文献１においては、ビピリジン誘導体の合成技術の容易性などに着目し、ビピリジン誘導体、特にビピリジンとベンゾイミダゾールとを組み合わせた化合物、ビピリジンの５，５'−位にベンゾイミダゾールを２位で結合した化合物を合成し、その化合物は極めて高効率で青色の強い発光を示した。また、前記構造の半分の構造を持つ、２−ピリジン−３−イル−１Ｈ−ベンゾイミダゾールにもかなり優れた発光特性を見出し、２−ピリジン−３−イル、５，５'−ビピリジルとベンゾイミダゾール−２−イルとの結合が、発光性を示す新規な基本骨格構造であることを開示した。また、特許文献２においては、さらに工業的により好適に応用させるために、発光物性が同程度以上の有機溶媒に溶解しやすい化学構造を持つビピリジン誘導体を開示している。
In Patent Document 1, paying attention to the ease of synthesis of bipyridine derivatives, bipyridine derivatives, particularly compounds combining bipyridine and benzimidazole, benzimidazole is bonded to the 5,5′-position of bipyridine at the 2-position. A compound was synthesized, and the compound showed very strong blue emission with very high efficiency. In addition, 2-pyridin-3-yl-1H-benzimidazole having a half structure of the above-mentioned structure has also been found to have considerably excellent luminescent properties, 2-pyridin-3-yl, 5,5′-bipyridyl and benzimidazole. It has been disclosed that the bond with 2-yl is a novel basic skeleton structure exhibiting luminescence. Further,
また、近年の有機ＥＬは高効率化の他に長寿命化も大きな課題であり、様々な研究が行なわれている。特に有機ＥＬの寿命を縮める原因の一つとしては、発光層を構成する有機化合物が酸素等に対して不安定であることが挙げられているが、発光層に酸素等の進入を遮断する方法で寿命を維持しているの現状である。従って有機ＥＬ発光材料としては、酸素等に対して安定であり、さらに発光物性が安定している有機発光性化合物が求められる。 In addition, in recent years, organic EL has a great problem of increasing the lifetime as well as improving efficiency, and various studies have been conducted. In particular, one of the causes for shortening the lifetime of the organic EL is that the organic compound constituting the light emitting layer is unstable with respect to oxygen or the like, but a method for blocking the entry of oxygen or the like into the light emitting layer. This is the current status of maintaining the service life. Accordingly, an organic EL light-emitting material that is stable against oxygen or the like and has stable light-emitting properties is required as the organic EL light-emitting material.
本発明は上記の状況に鑑み、酸素の影響を受けない優れた光物性を有する有機発光性化合物及びその化合物を含む発光層を提供する。 In view of the above situation, the present invention provides an organic light-emitting compound having excellent optical properties not affected by oxygen and a light-emitting layer containing the compound.
本発明者らは、上記課題を解決すべく鋭意検討した結果、ビピリジンとベンゾイミダゾールを骨格に有する化合物に高効率で強い発光を示す物性を見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the compound having bipyridine and benzimidazole in the skeleton has physical properties that exhibit high efficiency and strong light emission, and have completed the present invention.
すなわち、本発明は、以下の有機発光性化合物及びその化合物を含有する発光層に関する。
１．式（Ｉ）
Ｒ3、Ｒ'3、Ｒ4、及びＲ'4は、各々独立して水素原子；未置換、または窒素原子、酸素原子、硫黄原子及び／またはハロゲン原子を含んでもよいアルキル基、アルケニル基もしくはアルキニル基；及び未置換またはアルキル基、アリール基、アシル基、水酸基、アミノ基、スルホン酸基及び／またはハロゲン原子で置換されたアリール基からなる群から選択される基を表わし、
Ｘ1、Ｘ2、Ｘ'1、及びＸ'2は、各々独立して水素原子、アルキル基、アシル基、アリール基及びハロゲン原子からなる群から選択される基を表わし、
ｐ、ｑ、ｒ、ｐ'、ｑ'、及びｒ'は、各々独立して０または１を表わし、
ｍ、ｎ、ｍ'、及びｎ'は、各々独立して０または１〜３の整数を表わす。）
及び式（Ｉ）の異性体である式（Ｉ'）
で示されることを特徴とする有機発光性化合物。
２．式（II）
ｓ及びｓ'は、各々独立して０または１〜４の整数を表わし、
その他のすべての記号は前記と同じ意味を表わす。）
及び式（II）の異性体である式（II'）
で示される前記１に記載の有機発光性化合物。
３．式（III）
及び式（III）の異性体である式（III'）
で示される前記１または２に記載の有機発光性化合物。
４．式（IV）
で示される前記１〜３のいずれかに記載の有機発光性化合物。
５．式（Ｖ）
で示される前記１〜３のいずれかに記載の有機発光性化合物。
６．前記１〜５のいずれかに記載の有機発光性化合物を含有する発光層。
That is, this invention relates to the following organic luminescent compounds and the light emitting layer containing the compound.
1. Formula (I)
R 3 , R ′ 3 , R 4 , and R ′ 4 are each independently a hydrogen atom; an alkyl group, an alkenyl group, or an unsubstituted or optionally substituted nitrogen atom, oxygen atom, sulfur atom and / or halogen atom An alkynyl group; and a group selected from the group consisting of an unsubstituted or alkyl group, an aryl group, an acyl group, a hydroxyl group, an amino group, a sulfonic acid group and / or an aryl group substituted with a halogen atom,
X 1 , X 2 , X ′ 1 and X ′ 2 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, an acyl group, an aryl group and a halogen atom;
p, q, r, p ′, q ′, and r ′ each independently represent 0 or 1,
m, n, m ′, and n ′ each independently represent an integer of 0 or 1-3. )
And formula (I ′) which is an isomer of formula (I)
An organic light-emitting compound characterized by the following:
2. Formula (II)
s and s ′ each independently represents 0 or an integer of 1 to 4,
All other symbols have the same meaning as described above. )
And the formula (II ′) which is an isomer of the formula (II)
2. The organic light-emitting compound according to 1 above,
3. Formula (III)
And the formula (III ') which is an isomer of the formula (III)
3. The organic light-emitting compound according to 1 or 2 shown above.
4). Formula (IV)
The organic light-emitting compound according to any one of 1 to 3 represented by:
5. Formula (V)
The organic light-emitting compound according to any one of 1 to 3 represented by:
6). The light emitting layer containing the organic luminescent compound in any one of said 1-5.
本発明有機発光性化合物は、酸素の影響を受けることなく優れた光物性を維持し、高効率な発光特性を有するため、有機エレクトロルミネセンス（有機ＥＬ）発光材料等の用途に広く利用することができ、その長寿命化を可能にする。 The organic light-emitting compound of the present invention maintains excellent light physical properties without being affected by oxygen and has high-efficiency light-emitting characteristics, and therefore can be widely used for applications such as organic electroluminescence (organic EL) light-emitting materials. This makes it possible to extend its service life.
以下、本発明の実施の形態を具体的に説明する。
本発明の有機発光性化合物は、特許文献１及び特許文献２におけるビピリジン−イミダゾール骨格を単数または複数有する化合物であり、ビピリジン−イミダゾール骨格を複数有する場合は、特定のスペーサーを介してその骨格を連結した化合物である。
Hereinafter, embodiments of the present invention will be specifically described.
The organic light-emitting compound of the present invention is a compound having one or a plurality of bipyridine-imidazole skeletons in Patent Document 1 and
本発明の有機発光性化合物は、式（Ｉ）
Ｒ3、Ｒ'3、Ｒ4、及びＲ'4は、各々独立して水素原子；未置換、または窒素原子、酸素原子、硫黄原子及び／またはハロゲン原子を含んでもよいアルキル基、アルケニル基もしくはアルキニル基；及び未置換またはアルキル基、アリール基、アシル基、水酸基、アミノ基、スルホン酸基及び／またはハロゲン原子で置換されたアリール基からなる群から選択される基を表わし、
Ｘ1、Ｘ2、Ｘ'1、及びＸ'2は、各々独立して水素原子、アルキル基、アシル基、アリール基及びハロゲン原子からなる群から選択される基を表わし、
ｐ、ｑ、ｒ、ｐ'、ｑ'、及びｒ'は、各々独立して０または１を表わし、
ｍ、ｎ、ｍ'、及びｎ'は、各々独立して０または１〜３の整数を表わす。）
及び式（Ｉ）の異性体である式（Ｉ'）
で示される。
The organic light-emitting compound of the present invention has the formula (I)
R 3 , R ′ 3 , R 4 , and R ′ 4 are each independently a hydrogen atom; an alkyl group, an alkenyl group, or an unsubstituted or optionally substituted nitrogen atom, oxygen atom, sulfur atom and / or halogen atom An alkynyl group; and a group selected from the group consisting of an unsubstituted or alkyl group, an aryl group, an acyl group, a hydroxyl group, an amino group, a sulfonic acid group and / or an aryl group substituted with a halogen atom,
X 1 , X 2 , X ′ 1 and X ′ 2 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, an acyl group, an aryl group and a halogen atom;
p, q, r, p ′, q ′, and r ′ each independently represent 0 or 1,
m, n, m ′, and n ′ each independently represent an integer of 0 or 1-3. )
And formula (I ′) which is an isomer of formula (I)
Indicated by
本発明の有機発光性化合物として好ましくは、式（II）
ｓ及びｓ'は、各々独立して０または１〜４の整数を表わし、
その他のすべての記号は前記と同じ意味を表わす。）
及び式（II）の異性体である式（II'）
で示される有機発光性化合物である。
The organic light-emitting compound of the present invention is preferably represented by the formula (II)
s and s ′ each independently represents 0 or an integer of 1 to 4,
All other symbols have the same meaning as described above. )
And the formula (II ′) which is an isomer of the formula (II)
It is an organic luminescent compound shown by these.
本発明の有機発光性化合物としてさらに好ましくは、式（III）
及び式（III）の異性体である式（III'）
で示される有機発光性化合物であり、より好ましくは、式（IV）
及び式（Ｖ）
で示される有機発光性化合物である。
More preferably, the organic light-emitting compound of the present invention is represented by the formula (III)
And the formula (III ') which is an isomer of the formula (III)
An organic light-emitting compound represented by formula (IV), more preferably
And the formula (V)
It is an organic luminescent compound shown by these.
本発明有機発光性化合物の一好適例の合成方法の例を下記の反応工程式に示す。各反応工程自体は、既知の有機合成方法であるため、化合物は新規であるが、容易に合成することができる（Liebigs Ann. Chem. 1979, 1818-1827，特許文献１，特許文献２参照）。 An example of the synthesis method of a preferred example of the organic light-emitting compound of the present invention is shown in the following reaction process formula. Since each reaction step itself is a known organic synthesis method, the compound is novel, but can be easily synthesized (see Liebigs Ann. Chem. 1979, 1818-1827, Patent Document 1, Patent Document 2). .
本発明有機発光性化合物は、置換基の選択にもよるが、例えば吸収極大波長は３５０〜４００ｎｍ、発光極大波長は４８０〜５００ｎｍ、発光量子収率Φは０．８〜１．０であり、優れた光物性を有する。 Although the organic light-emitting compound of the present invention depends on the choice of substituent, for example, the absorption maximum wavelength is 350 to 400 nm, the emission maximum wavelength is 480 to 500 nm, and the emission quantum yield Φ is 0.8 to 1.0, Excellent optical properties.
本発明有機発光性化合物には、様々な用途があるが、中でも好適に用いられるのは、発光素子、有機ＥＬ素子に含まれる発光層、レーザー色素、発光性試薬等である。
本発明の有機発光性化合物を用いる発光層は、一般に行なわれる方法で製造することができ、特に制限されない。例えば、本発明の有機発光性化合物を溶媒に溶解させ、ディップコーティング、スピンコーティング等の塗布法、各種の印刷法、またはインクジェット法により、成膜または画素として形成できる。本発明の有機発光性化合物を用いる発光層は、例えば発光素子等に使用することが可能である。
The organic light-emitting compound of the present invention has various uses. Among them, a light-emitting element, a light-emitting layer contained in the organic EL element, a laser dye, a light-emitting reagent, and the like are preferably used.
The light emitting layer using the organic light emitting compound of the present invention can be produced by a generally performed method, and is not particularly limited. For example, the organic light-emitting compound of the present invention can be dissolved in a solvent and formed as a film or a pixel by a coating method such as dip coating or spin coating, various printing methods, or an ink jet method. The light emitting layer using the organic light emitting compound of the present invention can be used for, for example, a light emitting element.
以下、本発明を実施例を用いて説明するが、以下の例は、本発明を説明するためのものであり、本発明を限定するものではない。 EXAMPLES Hereinafter, although this invention is demonstrated using an Example, the following examples are for demonstrating this invention, and do not limit this invention.
実施例１：
［Bis(Bzim(C6)-bpy)-Bzdim(C6)-Eの合成］
（１）Ｎ−ヘキシル−２−ニトロアニリンの合成
[Synthesis of Bis (Bzim (C 6 ) -bpy) -Bzdim (C 6 ) -E]
(1) Synthesis of N-hexyl-2-nitroaniline
（２）Ｎ−ヘキシル−１，２−フェニレンジアミンの合成
（３）２，２'−ビピリジン−５，５'−ジカルボン酸の合成
（４）２，２'−ビピリジン−５，５'−ジカルボン酸エチルエステルの合成
（５）２，２'−ビピリジン−５−カルボン酸−５'−カルボン酸エチルエステル（HOOC-bpy-COOEt）の合成
同定：1Ｈ−ＮＭＲ（300 MHz, DMSO-d6）；
δ 9.210 - 9.185 (m, 2H), 8.600 - 8.549 (m, 2H), 8.484 - 8.429 (m, 2H), 4.379 (q, 2H), 1.355 (t, 3H).
ＥＩ−ＭＳ（m/z）Calcd for M+ C14H12N2O4: 272.08, found: 272.
(5) Synthesis of 2,2′-bipyridine-5-carboxylic acid-5′-carboxylic acid ethyl ester (HOOC-bpy-COOEt)
Identification: 1 H-NMR (300 MHz, DMSO-d 6 );
δ 9.210-9.185 (m, 2H), 8.600-8.549 (m, 2H), 8.484-8.429 (m, 2H), 4.379 (q, 2H), 1.355 (t, 3H).
EI-MS (m / z) Calcd for M + C 14 H 12 N 2 O 4 : 272.08, found: 272.
（６）５−（１Ｎ−ヘキシル−ベンゾイミダゾール−２−イル）−２，２'−ビピリジン−５'−カルボン酸エチルエステル（Bzim(C6)-bpy-COOEt）の合成
同定：1Ｈ−ＮＭＲ（300 MHz, CDCl3）；
δ 9.321 (dd, J = 0.6, 2.1 Hz, 1H), 9.075 (dd, J = 0.6, 2.2 Hz, 1H), 8.672 (dd, J = 0.6, 8.1 Hz, 1H), 8.594 (dd, J = 0.7, 8.2 Hz, 1H), 8.457 (dd, J = 2.1, 8.3 Hz, 1H), 8.260 (dd, J = 2.3, 8.3 Hz, 1H), 7.891 - 7.839 (m, 1H), 7.477 - 7.424 (m, 1H), 7.397 - 7.302 (m, 2H), 4.463 (q, 2H), 4.292 (t, 2H), 1.895 - 1.821 (m, 2H), 1.454 (t, 3H), 1.319 - 1.216 (m, 6H), 0.857 - 0.813 (m, 3H).
ＥＩ−ＭＳ（m/z）Calcd for M+ C26H28N4O2: 428.22, found: 428.
(6) Synthesis of 5- (1N-hexyl-benzimidazol-2-yl) -2,2′-bipyridine-5′-carboxylic acid ethyl ester (Bzim (C 6 ) -bpy-COOEt)
Identification: 1 H-NMR (300 MHz, CDCl 3 );
δ 9.321 (dd, J = 0.6, 2.1 Hz, 1H), 9.075 (dd, J = 0.6, 2.2 Hz, 1H), 8.672 (dd, J = 0.6, 8.1 Hz, 1H), 8.594 (dd, J = 0.7 , 8.2 Hz, 1H), 8.457 (dd, J = 2.1, 8.3 Hz, 1H), 8.260 (dd, J = 2.3, 8.3 Hz, 1H), 7.891-7.839 (m, 1H), 7.477-7.424 (m, 1H), 7.397-7.302 (m, 2H), 4.463 (q, 2H), 4.292 (t, 2H), 1.895-1.821 (m, 2H), 1.454 (t, 3H), 1.319-1.216 (m, 6H) , 0.857-0.813 (m, 3H).
EI-MS (m / z) Calcd for M + C 26 H 28 N 4 O 2 : 428.22, found: 428.
（７）５−（１Ｎ−ヘキシル−ベンゾイミダゾール−２−イル）−２，２'−ビピリジン−５'−カルボン酸（Bzim(C6)-bpy-COOH）の合成
同定：1Ｈ−ＮＭＲ（300 MHz, DMSO-d6）；
δ 9.201 (dd, J = 2.1, 10.7 Hz, 2H), 8.938 (d, J = 8.4 Hz, 1H), 8.897 (d, J = 8.3 Hz, 1H), 8.475 (dd, J = 2.1, 8.3 Hz, 2H), 7.8993 - 7.8074 (m, 2H), 7.4814 - 7.4348 (m, 2H), 4.4664 - 4.4166 (m, 2H), 1.7292 - 1.7292 (m, 2H), 1.1273 - 1.0744 (m, 6H), 0.7438 - 0.7005 (m, 3H).
(7) Synthesis of 5- (1N-hexyl-benzimidazol-2-yl) -2,2′-bipyridine-5′-carboxylic acid (Bzim (C 6 ) -bpy-COOH)
Identification: 1 H-NMR (300 MHz, DMSO-d 6 );
δ 9.201 (dd, J = 2.1, 10.7 Hz, 2H), 8.938 (d, J = 8.4 Hz, 1H), 8.897 (d, J = 8.3 Hz, 1H), 8.475 (dd, J = 2.1, 8.3 Hz, 2H), 7.8993-7.8074 (m, 2H), 7.4814-7.4348 (m, 2H), 4.4664-4.4166 (m, 2H), 1.7292-1.7292 (m, 2H), 1.1273-1.0744 (m, 6H), 0.7438- 0.7005 (m, 3H).
（８）２，６−ビス［５'−（１−ヘキシル−ベンゾイミダゾール−２−イル）−２，２'−ビピリジル−５−イル］−１，５−ジヒドロ−ベンゾ［１，２−ｄ：４，５−ｄ'］ジイミダゾール（Bis(Bzim(C6)-bpy)-Bzdim(H)）の合成
同定：ＦＡＢ−ＭＳ（m/z）Calcd for M+ C54H51N12: 866.43, found: 867.4360.
(8) 2,6-bis [5 ′-(1-hexyl-benzimidazol-2-yl) -2,2′-bipyridyl-5-yl] -1,5-dihydro-benzo [1,2-d : 4,5-d ′] diimidazole (Bis (Bzim (C 6 ) -bpy) -Bzdim (H))
Identification: FAB-MS (m / z) Calcd for M + C 54 H 51 N 12 : 866.43, found: 867.4360.
（９）Bis(Bzim(C6)-bpy)-Bzdim(C6)-Eの合成
同定（Bis(Bzim(C6)-bpy)-Bzdim(C6)-E）：1Ｈ−ＮＭＲ（600 MHz, CDCl3）；
δ 9.172 (d, J = 1.8 Hz, 2H), 9.110 (d, J = 1.8 Hz, 2H), 8.722 (d, J = 7.8 Hz, 2H), 8.709 (d, J = 7.8 Hz, 2H), 8.350 (dd, J = 2.4, 8.4 Hz, 2H), 8.297 (dd, J = 1.8, 8.1 Hz, 2H), 7.890 - 7.879 (m, 2H), 8.874 (s, 2H), 7.483 - 7.468 (m, 2H), 7.391 - 7.347 (m, 4H), 4.409 (t, 4H), 4.319 (t, 4H), 1.981 (quintet, 4H), 1.895 (quintet, 4H), 1.369 - 1.247 (m, 24H), 0.870 - 0.843 (m, 12H).
ＳＩ−ＭＳ（m/z）Calcd for M+ C66H74N12: 1034.62, found: 1035.
(9) Synthesis of Bis (Bzim (C 6 ) -bpy) -Bzdim (C 6 ) -E
Identification (Bis (Bzim (C 6) -bpy) -Bzdim (C 6) -E): 1 H-NMR (600 MHz, CDCl 3);
δ 9.172 (d, J = 1.8 Hz, 2H), 9.110 (d, J = 1.8 Hz, 2H), 8.722 (d, J = 7.8 Hz, 2H), 8.709 (d, J = 7.8 Hz, 2H), 8.350 (dd, J = 2.4, 8.4 Hz, 2H), 8.297 (dd, J = 1.8, 8.1 Hz, 2H), 7.890-7.879 (m, 2H), 8.874 (s, 2H), 7.483-7.468 (m, 2H ), 7.391-7.347 (m, 4H), 4.409 (t, 4H), 4.319 (t, 4H), 1.981 (quintet, 4H), 1.895 (quintet, 4H), 1.369-1.247 (m, 24H), 0.870- 0.843 (m, 12H).
SI-MS (m / z) Calcd for M + C 66 H 74 N 12 : 1034.62, found: 1035.
［Bis(Bzim(C6)-bpy)-Bzdim(C6)-Eの光物性］
Bis(Bzim(C6)-bpy)-Bzdim(C6)-Eの吸収極大３６２ｎｍにおける吸光度が０．０５６４のアセトニトリル溶液をつくり、アルゴン下、吸収、蛍光スペクトルを測定した（図１）。３６２ｎｍ励起に対して、発光極大は４９９ｎｍであり、5,5'-Bzim(H)-bpyのメタノール溶液における発光極大（４４５ｎｍ）よりかなり長波長側に観測された。空気中において発光スペクトルを測定すると、アルゴン下とほとんど変わらないことから（図２中、点線：空気下、実線：アルゴン下）、この発光はほとんど酸素による影響を受けない、励起一重項からの蛍光発光であると考えられる。また、９，１０−ジフェニルアントラセン（シクロヘキサン溶液）を基準として、３６２ｎｍでの励起による発光量子収率を測定すると０．９３であり、高効率な発光特性を維持していることが明らかとなった。吸収スペクトルにおけるモル吸光係数（ε）は、アセトニトリル中では溶解度が低く、正確に求めることができなかったため、クロロホルム溶液を用いて測定した。クロロホルム中では極大波長は３６５ｎｍであり、εは７．１９×１０4Ｍ-1ｃｍ-1と求められた。
Bis(Bzim(C6)-bpy)-Bzdim(C6)-EのＭｅＯＨ／ＥｔＯＨ（１：４（ｖ／ｖ））溶液を調製し、アルゴン雰囲気下、３５７ｎｍ励起による吸収蛍光スペクトルを測定したところ、発光極大は５０１ｎｍであった（図３）。また、この溶液を用いて７７Ｋにおける励起発光スペクトルを測定したところ、発光極大波長（０−０）は４１５ｎｍであった（図４）。
[Optical properties of Bis (Bzim (C 6 ) -bpy) -Bzdim (C 6 ) -E]
A solution of Bis (Bzim (C 6 ) -bpy) -Bzdim (C 6 ) -E having an absorbance maximum at 362 nm of 0.0564 was prepared, and absorption and fluorescence spectra were measured under argon (FIG. 1). For 362 nm excitation, the emission maximum was 499 nm, which was observed on a considerably longer wavelength side than the emission maximum (445 nm) in a methanol solution of 5,5′-Bzim (H) -bpy. Since the emission spectrum measured in air is almost the same as that under argon (in FIG. 2, dotted line: under air, solid line: under argon), this emission is hardly affected by oxygen. Fluorescence from excited singlet It is considered to be luminescence. Further, when the emission quantum yield by excitation at 362 nm was measured with 9,10-diphenylanthracene (cyclohexane solution) as a reference, it was 0.93, and it was revealed that highly efficient emission characteristics were maintained. . The molar extinction coefficient (ε) in the absorption spectrum was measured using a chloroform solution because the solubility in acetonitrile was low and could not be determined accurately. In chloroform, the maximum wavelength was 365 nm, and ε was determined to be 7.19 × 10 4 M −1 cm −1 .
A solution of Bis (Bzim (C 6 ) -bpy) -Bzdim (C 6 ) -E in MeOH / EtOH (1: 4 (v / v)) was prepared, and the absorption fluorescence spectrum by 357 nm excitation was measured in an argon atmosphere. However, the emission maximum was 501 nm (FIG. 3). Moreover, when the excitation light emission spectrum in 77K was measured using this solution, the light emission maximum wavelength (0-0) was 415 nm (FIG. 4).
実施例２：
［Bis(Bzim(C6)-bpy)-Bzdim(C6)-Zの合成］
実施例１の段階（１）〜（８）と同様に行い、段階（９）のシリカゲルカラムクロマトグラフィー（溶離液：ＣＨＣｌ3／５％−ＣＨ3ＯＨ，２．８φｃｍ×２２．５ｃｍ）によりBis(Bzim(C6)-bpy)-Bzdim(C6)-Zを分離し、酢酸エチルで再結晶を行い、精製したBis(Bzim(C6)-bpy)-Bzdim(C6)-Zが得られた。
同定（Bis(Bzim(C6)-bpy)-Bzdim(C6)-Z）：1Ｈ−ＮＭＲ（600 MHz, CDCl3）；
δ 9.157 (d, J = 1.8 Hz, 2H), 9.108 (d, J = 1.8 Hz, 2H), 8.717 (d, J = 5.4 Hz, 2H), 8.704 (d, J = 5.4 Hz, 2H), 8.328 (dd, J = 2.4, 39 Hz, 2H), 8.343 (s, 1H), 8.297 (dd, J = 1.8, 7.8 Hz, 2H), 7.484 - 7.47 (m, 2H), 7.378 - 7.357 (m, 4H), 7.335 (s, 1H), 4.424 (t, 4H), 4.319 (t, 4H), 1.956 (quintet, 4H), 1.895 (quintet, 4H), 1.355 - 1.254 (m, 24H), 0.874 - 0.842 (m, 12H).
ＳＩ−ＭＳ（m/z）Calcd for M+ C66H74N12: 1034.62, found: 1035.
Example 2:
[Synthesis of Bis (Bzim (C 6 ) -bpy) -Bzdim (C 6 ) -Z]
Performed in the same manner as in steps (1) to (8) of Example 1, and Bis was performed by silica gel column chromatography (eluent: CHCl 3 /5% -CH 3 OH, 2.8 φcm × 22.5 cm) in step (9). (Bzim (C 6 ) -bpy) -Bzdim (C 6 ) -Z was separated, recrystallized with ethyl acetate, and purified Bis (Bzim (C 6 ) -bpy) -Bzdim (C 6 ) -Z Obtained.
Identification (Bis (Bzim (C 6) -bpy) -Bzdim (C 6) -Z): 1 H-NMR (600 MHz, CDCl 3);
δ 9.157 (d, J = 1.8 Hz, 2H), 9.108 (d, J = 1.8 Hz, 2H), 8.717 (d, J = 5.4 Hz, 2H), 8.704 (d, J = 5.4 Hz, 2H), 8.328 (dd, J = 2.4, 39 Hz, 2H), 8.343 (s, 1H), 8.297 (dd, J = 1.8, 7.8 Hz, 2H), 7.484-7.47 (m, 2H), 7.378-7.357 (m, 4H ), 7.335 (s, 1H), 4.424 (t, 4H), 4.319 (t, 4H), 1.956 (quintet, 4H), 1.895 (quintet, 4H), 1.355-1.254 (m, 24H), 0.874-0.842 ( m, 12H).
SI-MS (m / z) Calcd for M + C 66 H 74 N 12 : 1034.62, found: 1035.
［Bis(Bzim(C6)-bpy)-Bzdim(C6)-Zの光物性］
Bis(Bzim(C6)-bpy)-Bzdim(C6)-Zの吸収極大３６０ｎｍにおける吸光度が０．０６７２のアセトニトリル溶液をつくり、アルゴン下、吸収、蛍光スペクトルを測定した（図５）。３６０ｎｍ励起に対して、発光スペクトルは４８６ｎｍに極大をもち、Ｅ体（１９９ｎｍ）よりやや短波長側であった。実施例１のＥ体と同様に、空気下でのスペクトルを測定したが、アルゴン下と同様であり、ほとんど酸素の影響を受けない励起一重項からの蛍光発光であると考えられる（図６）。９，１０−ジフェニルアントラセン（シクロヘキサン溶液）を基準として、３６０ｎｍでの励起による発光量子収率は０．８０と求められ、高効率な発光特性を維持しているものの、実施例１のＥ体よりやや発光効率が低下し、スペーサー部分のベンゾジイミダゾール誘導体の構造が発光特性に影響することが示唆された。吸収スペクトルにおけるモル吸光係数（ε）は、実施例１のＥ体と同様に、アセトニトリル中では溶解度が低く、正確に求めることができなかったため、クロロホルム溶液を用いて測定した。クロロホルム中では極大波長は３６３ｎｍであり、εは８．４５×１０4Ｍ-1ｃｍ-1と求められた。
さらに、Bis(Bzim(C6)-bpy)-Bzdim(C6)-ZのＭｅＯＨ／ＥｔＯＨ（１：４（ｖ／ｖ））溶液を調製し、アルゴン雰囲気下、３５４ｎｍ励起による吸収蛍光スペクトルを測定したところ、発光極大は４９９ｎｍであった（図７）。また、この溶液を用いて７７Ｋにおける励起発光スペクトルを測定したところ、発光極大波長（０−０）は４０８ｎｍであった（図８）。
[Optical properties of Bis (Bzim (C 6 ) -bpy) -Bzdim (C 6 ) -Z]
A solution of Bis (Bzim (C 6 ) -bpy) -Bzdim (C 6 ) -Z having an absorbance maximum at 360 nm of 0.0672 was prepared, and absorption and fluorescence spectra were measured under argon (FIG. 5). For 360 nm excitation, the emission spectrum had a maximum at 486 nm, slightly shorter than the E body (199 nm). The spectrum under air was measured in the same manner as in the E body of Example 1, but it was the same as under argon, and it was considered that the fluorescence was emitted from an excited singlet that was hardly affected by oxygen (FIG. 6). . Based on 9,10-diphenylanthracene (cyclohexane solution), the emission quantum yield by excitation at 360 nm is determined to be 0.80, and while maintaining highly efficient emission characteristics, It was suggested that the luminous efficiency was slightly lowered, and that the structure of the benzodiimidazole derivative in the spacer part affects the luminescent properties. The molar extinction coefficient (ε) in the absorption spectrum was measured using a chloroform solution because the solubility in acetonitrile was low and could not be determined accurately, as in the E form of Example 1. In chloroform, the maximum wavelength was 363 nm, and ε was determined to be 8.45 × 10 4 M −1 cm −1 .
Furthermore, a solution of Bis (Bzim (C 6 ) -bpy) -Bzdim (C 6 ) -Z in MeOH / EtOH (1: 4 (v / v)) was prepared, and the absorption fluorescence spectrum by 354 nm excitation was obtained in an argon atmosphere. When measured, the emission maximum was 499 nm (FIG. 7). Moreover, when the excitation light emission spectrum in 77K was measured using this solution, the light emission maximum wavelength (0-0) was 408 nm (FIG. 8).
実施例３：
［Bis(Bzim(C6)-bpy)-Bzdim(H)の合成］
実施例１の段階（１）〜（７）と同様に行い、段階（８）において精製したBis(Bzim(C6)-bpy)-Bzdim(H)が得られた。
Example 3:
[Synthesis of Bis (Bzim (C 6 ) -bpy) -Bzdim (H)]
Bis (Bzim (C 6 ) -bpy) -Bzdim (H) purified in the same manner as in steps (1) to (7) of Example 1 was obtained.
［Bis(Bzim(C6)-bpy)-Bzdim(H)の光物性］
Bis(Bzim(C6)-bpy)-Bzdim(H)の吸収極大３９５ｎｍにおける吸光度が０．１以下のＣＨＣｌ3／ＭｅＯＨ（９：１（ｖ／ｖ））溶液を調製し、アルゴン下、吸収、蛍光スペクトルを測定した。３９５ｎｍ励起に対して、発光スペクトルは４８８ｎｍに極大をもち、実施例１及び２と同様に、空気下でのスペクトルを測定したが、アルゴン下と同様であり、ほとんど酸素の影響を受けない励起一重項からの蛍光発光であると考えられる。９，１０−ジフェニルアントラセン（シクロヘキサン溶液）を基準として、３９５ｎｍでの励起による発光量子収率は０．８８〜１．０８と求められた。
[Optical properties of Bis (Bzim (C 6 ) -bpy) -Bzdim (H)]
A CHCl 3 / MeOH (9: 1 (v / v)) solution having an absorbance maximum at 395 nm of Bis (Bzim (C 6 ) -bpy) -Bzdim (H) of 0.1 or less was prepared and absorbed under argon The fluorescence spectrum was measured. For 395 nm excitation, the emission spectrum has a maximum at 488 nm, and the spectrum under air was measured in the same manner as in Examples 1 and 2, but it was the same as under argon and was almost unaffected by oxygen. Fluorescence emission from the term is considered. Based on 9,10-diphenylanthracene (cyclohexane solution), the emission quantum yield by excitation at 395 nm was determined to be 0.88 to 1.08.
参考例１〜５：
下記に示す化合物を特許文献１及び特許文献２を参考にして合成し、実施例１〜３と同様に光物性について測定した（表１）。
The compounds shown below were synthesized with reference to Patent Document 1 and
［光物性のまとめ］
実施例１〜３及び参考例１〜５において合成した各化合物の光物性を表１に示す。
Table 1 shows the optical properties of the compounds synthesized in Examples 1 to 3 and Reference Examples 1 to 5.
Claims (5)
（式中の記号は前記と同じ意味を表す。）
で示されることを特徴とする有機発光性化合物。 Formula (IV)
(The symbols in the formula have the same meaning as described above.)
An organic light-emitting compound characterized by the following:
で示される請求項１に記載の有機発光性化合物。 Formula (IV)
The organic light emitting compound of Claim 1 shown by these.
（式中の記号は前記と同じ意味を表す。）
で示される請求項１に記載の有機発光性化合物。 Formula (V)
(The symbols in the formula have the same meaning as described above.)
The organic light emitting compound of Claim 1 shown by these.
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