WO2022009930A1 - Light-emitting material, light-emitting ink, light-emitting body, and light-emitting device - Google Patents

Light-emitting material, light-emitting ink, light-emitting body, and light-emitting device Download PDF

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WO2022009930A1
WO2022009930A1 PCT/JP2021/025663 JP2021025663W WO2022009930A1 WO 2022009930 A1 WO2022009930 A1 WO 2022009930A1 JP 2021025663 W JP2021025663 W JP 2021025663W WO 2022009930 A1 WO2022009930 A1 WO 2022009930A1
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靖哉 長谷川
テン ツァン
裕一 北川
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国立大学法人北海道大学
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract

Disclosed is a light-emitting material including: a substrate that includes a metal oxide and/or a metal sulfide; two or more linker groups bonded to the substrate; a phosphine oxide ligand bonded to each of the linker groups, each phosphine oxide ligand having a single phosphine oxide group; and a rare earth ion. A rare earth complex is formed by a single rare earth ion and two or more phosphine oxide ligands.

Description

発光材料、発光インク、発光体及び発光デバイスLuminescent material, luminescent ink, luminescent material and luminescent device
　本開示は、発光材料、発光インク、発光体及び発光デバイスに関する。 The present disclosure relates to light emitting materials, light emitting inks, light emitting bodies and light emitting devices.
　シリカ等を含む基材上に発光性の希土類錯体を固定することが試みられている（例えば特許文献１、非特許文献１）。 Attempts have been made to immobilize a luminescent rare earth complex on a substrate containing silica or the like (for example, Patent Document 1 and Non-Patent Document 1).
　特許文献１は、多孔質シリカに硝酸アルミニウム水溶液及び硝酸ユーロピウム水溶液を添加し混合後、乾燥及び焼成して得た焼成物に、シランカップリング剤で表面処理をして蛍光体を得る方法を開示する。アルミニウム及びユーロピウムはシリカ上に固定されているものの、それがどのような形式であるかは明らかでなく不均一に付着しているものと考えられる。 Patent Document 1 discloses a method for obtaining a phosphor by surface-treating a fired product obtained by adding an aqueous solution of aluminum nitrate and an aqueous solution of europium nitrate to porous silica, mixing them, drying and firing them with a silane coupling agent. do. Although aluminum and europium are fixed on silica, it is not clear what kind of form they are, and it is considered that they adhere unevenly.
　非特許文献１、２は、ホスフィンオキシド配位子又はビピリジン配位子のような二座配位子が１つのリンカー基を介してシリカに結合したユーロピウム錯体含有粒子を開示する。 Non-Patent Documents 1 and 2 disclose europium complex-containing particles in which a bidentate ligand such as a phosphine oxide ligand or a bipyridine ligand is bonded to silica via one linker group.
国際公開第２０１８／０３７９１４号International Publication No. 2018/037914
　基材上に固定された希土類錯体を含む従来の発光材料は、固定されない希土類錯体と比較して低い発光量子効率を示す傾向があった。そこで本開示の一側面は、基材上に固定された希土類錯体を含み、高い発光量子効率示す新規な発光材料を提供する。 Conventional luminescent materials containing rare earth complexes immobilized on a substrate tended to exhibit lower luminescence quantum efficiency than non-fixed rare earth complexes. Therefore, one aspect of the present disclosure provides a novel luminescent material containing a rare earth complex immobilized on a substrate and exhibiting high luminescence quantum efficiency.
　本開示の一側面は、金属酸化物又は金属硫化物のうち少なくとも一方を含む基材と、前記基材に結合した２以上のリンカー基と、それぞれの前記リンカー基に結合した、１つのホスフィンオキシド基を有するホスフィンオキシド配位子と、希土類イオンとを含む発光材料を提供する。１つの前記希土類イオンと２以上の前記ホスフィンオキシド配位子とで希土類錯体が形成されている。 One aspect of the present disclosure is a substrate containing at least one of a metal oxide or a metal sulfide, two or more linker groups attached to the substrate, and one phosphine oxide attached to each of the linker groups. Provided is a luminescent material containing a phosphine oxide ligand having a group and a rare earth ion. A rare earth complex is formed by one of the rare earth ions and two or more of the phosphine oxide ligands.
　本開示の別の一側面は、上記発光材料と、前記発光材料が分散した分散媒と、を含む、発光インクを提供する。 Another aspect of the present disclosure is to provide a luminescent ink comprising the luminescent material and a dispersion medium in which the luminescent material is dispersed.
　本開示の更に別の一側面は、上記発光材料を含む発光体、及び、発光体を備える発光デバイスを提供する。 Yet another aspect of the present disclosure is to provide a light emitting body containing the above light emitting material and a light emitting device including the light emitting body.
　本開示の一側面によれば、基材上に固定された希土類錯体を含み、高い発光量子効率示す新規な発光材料が提供される。 According to one aspect of the present disclosure, a novel luminescent material containing a rare earth complex immobilized on a substrate and exhibiting high luminescence quantum efficiency is provided.
シリカナノ粒子の透過型電子顕微鏡写真である。It is a transmission electron micrograph of silica nanoparticles. シリカナノ粒子及び希土類錯体を含む発光材料の透過型電子顕微鏡写真である。It is a transmission electron micrograph of a light emitting material containing silica nanoparticles and a rare earth complex. シリカナノ粒子及び希土類錯体を含む発光材料のＥＤＳスペクトルである。It is an EDS spectrum of a light emitting material containing silica nanoparticles and a rare earth complex. 発光材料又は希土類錯体のＦＴ－ＩＲスペクトルである。FT-IR spectrum of a luminescent material or a rare earth complex. 配位子、希土類錯体又は発光材料の励起スペクトルである。It is an excitation spectrum of a ligand, a rare earth complex or a luminescent material. 発光材料又は希土類錯体の発光スペクトルである。It is an emission spectrum of a light emitting material or a rare earth complex. 発光材料又は希土類錯体の発光減衰を示すグラフである。It is a graph which shows the emission attenuation of a light emitting material or a rare earth complex.
　本発明は以下に説明される例に限定されるものではない。 The present invention is not limited to the examples described below.
　発光材料の一例は、金属酸化物又は金属硫化物のうち少なくとも一方を含む基材と、基材に結合した２以上のリンカー基と、及び該リンカー基に結合した、１つのホスフィンオキシド基を有する複数のホスフィンオキシド配位子と、複数の希土類イオンとを含む。１つの希土類イオンと２以上のホスフィンオキシド配位子とで希土類錯体が形成されている。 An example of a luminescent material has a substrate containing at least one of a metal oxide or a metal sulfide, two or more linker groups attached to the substrate, and one phosphine oxide group attached to the linker group. Contains multiple phosphine oxide ligands and multiple rare earth ions. A rare earth complex is formed by one rare earth ion and two or more phosphine oxide ligands.
　下記化学式（Ｉ）は、発光材料の一例を模式的に示す。
Figure JPOXMLDOC01-appb-C000001
 The following chemical formula (I) schematically shows an example of a light emitting material.
Figure JPOXMLDOC01-appb-C000001
　式（Ｉ）中、Ｘは基材を示し、Ｌは基材Ｘ及びホスフィンオキシド配位子（（Ａｒ１）（Ａｒ２）Ｐ＝Ｏ）に結合したリンカー基を示し、Ｌｎ（ＩＩＩ）は希土類イオンを示す。Ａｒ１及びＡｒ２は、それぞれ独立に、置換基を有していてもよいアリール基を示す。Ｚは希土類イオンＬｎ（ＩＩＩ）と配位結合を形成しているｎ座の配位子を示す。式（Ｉ）において、１つの希土類イオンＬｎ（ＩＩＩ）、２つのホスフィンオキシド配位子、及び６／ｎ個の配位子Ｚとで希土類錯体が形成されている。１つのリンカー基Ｌに結合したホスフィンオキシド基の数は、典型的には１つである。式（Ｉ）では１つの希土類錯体のみが図示されているが、通常、多数の希土類錯体がリンカー基Ｌを介して基材Ｘに結合している。本発明者らの知見によれば、２つ以上のリンカー基を介して基材Ｘ上に希土類錯体を固定することで、基材Ｘ上に希土類錯体が安定的に固定化され、基材に固定されない希土類錯体と比較して、より高い量子収率で発光し得る。 In formula (I), X represents a substrate, L represents a substrate X and a linker group attached to a phosphine oxide ligand ((Ar 1 ) (Ar 2 ) P = O), and Ln (III) is Shows rare earth ions. Ar 1 and Ar 2 each independently represent an aryl group which may have a substituent. Z indicates an n-position ligand forming a coordinate bond with the rare earth ion Ln (III). In formula (I), a rare earth complex is formed with one rare earth ion Ln (III), two phosphine oxide ligands, and 6 / n ligands Z. The number of phosphine oxide groups attached to one linker group L is typically one. Although only one rare earth complex is shown in the formula (I), a large number of rare earth complexes are usually bonded to the base material X via the linker group L. According to the findings of the present inventors, by immobilizing the rare earth complex on the base material X via two or more linker groups, the rare earth complex is stably immobilized on the base material X, and the rare earth complex is stably immobilized on the base material X. It can emit light with a higher quantum yield compared to unfixed rare earth complexes.
　基材Ｘの形状は特に限定されず、例えば基材Ｘが粒子、フィルム又は板状体であってもよい。基材Ｘが粒子である場合、通常、希土類錯体が導入された発光材料も粒子状である。粒子状の発光材料は、例えば、発光インク、又は、バイオメディカル分野で用いられる蛍光粒子としての応用が期待される。基材としてのフィルムは、例えばプラスチックフィルムであってもよい。基材としての板状体は、例えばガラス板であってもよい。 The shape of the base material X is not particularly limited, and for example, the base material X may be a particle, a film, or a plate-like body. When the base material X is a particle, the light emitting material into which the rare earth complex is introduced is also usually in the form of particles. The particulate luminescent material is expected to be applied as, for example, a luminescent ink or fluorescent particles used in the biomedical field. The film as a base material may be, for example, a plastic film. The plate-like body as the base material may be, for example, a glass plate.
　基材Ｘが粒子である場合、その平均粒径が１０００ｎｍ以下、５００ｎｍ以下、又は１００ｎｍ以下であってもよく、１０ｎｍ以上であってもよい。ナノオーダーの粒径を有するナノ粒子を基材Ｘとして有する粒子状の発光材料は、各種の分散媒に対して良好な分散性を有し易い。希土類錯体が導入された発光材料の粒子径が、１０００ｎｍ以下、５００ｎｍ以下、又は１００ｎｍ以下であってもよく、１０ｎｍ以上であってもよい。 When the base material X is a particle, its average particle size may be 1000 nm or less, 500 nm or less, or 100 nm or less, or 10 nm or more. A particulate light-emitting material having nanoparticles having a nano-order particle size as a base material X tends to have good dispersibility with respect to various dispersion media. The particle size of the light emitting material into which the rare earth complex is introduced may be 1000 nm or less, 500 nm or less, or 100 nm or less, or 10 nm or more.
　基材Ｘは金属酸化物、金属硫化物又はこれらの両方を含む。金属酸化物の例としては、二酸化ケイ素（シリカ）、酸化亜鉛、酸化カルシウム、酸化チタン、酸化アルミニウム、及び酸化インジウムスズ（ＩＴＯ）が挙げられる。金属硫化物の例としては、硫化亜鉛及び硫化カドミウムが挙げられる。基材Ｘが、ガラス体（例えば、シリカガラス、ＩＴＯガラス、フッ素ガラス）、又は結晶であってもよい。基材Ｘにおける金属酸化物及び金属硫化物の合計の含有量は、基材Ｘの質量を基準として５０～１００質量％、６０～１００質量％、７０～１００質量％、８０～１００質量％、又は９０～１００質量％であってもよい。 Base material X contains metal oxides, metal sulfides, or both. Examples of metal oxides include silicon dioxide (silica), zinc oxide, calcium oxide, titanium oxide, aluminum oxide, and indium tin oxide (ITO). Examples of metal sulfides include zinc sulfide and cadmium sulfide. The base material X may be a glass body (for example, silica glass, ITO glass, fluorine glass) or a crystal. The total content of metal oxides and metal sulfides in the base material X is 50 to 100% by mass, 60 to 100% by mass, 70 to 100% by mass, 80 to 100% by mass, based on the mass of the base material X. Alternatively, it may be 90 to 100% by mass.
　リンカー基Ｌは、基材Ｘの金属酸化物又は金属硫化物と結合を形成している官能基を有する。官能基は、例えば加水分解性シリル基の残基であることができる。リンカー基Ｌが、ホスフィンオキシド基と結合したアリーレン基を更に有していてもよい。加水分解性シリル基の残基及びアリーレン基を含むリンカー基は、例えば下記式（１）で表される基のうち、Ｘを除く部分であってもよい。 The linker group L has a functional group forming a bond with the metal oxide or metal sulfide of the base material X. The functional group can be, for example, a residue of a hydrolyzable silyl group. The linker group L may further have an arylene group bonded to a phosphine oxide group. The linker group containing the residue of the hydrolyzable silyl group and the arylene group may be, for example, a portion of the group represented by the following formula (1) excluding X.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　式（１）中、Ｘは基材を示し、Ｒ１は２価の有機基を示し、Ｒ２は炭素数１～５、又は１～３のアルキル基を示し、Ａｒ３はホスフィンオキシド基と結合しているアリーレン基（例えばフェニレン基、ビフェニレン基、ナフチレン基）を示す。ｐはＳｉに結合した３つの酸素原子のうち基材Ｘと結合しているものの数に対応する１～３の整数を示す。＊はホスフィンオキシド基のリン原子と結合している部分を示す。Ｒ１は、通常、リンカー基を誘導する合成経路に由来する有機基である。例えば、Ｒ１がアミド基を含む基であってもよく、その場合のリンカー基Ｌの一例は下記式（１ａ）で表される。式（１ａ）中のＲ３はアルキレン基を示す。Ｒ３としてのアルキレン基の炭素数は、例えば、１以上又は２以上であってもよく、２０以下、１５以下又は１０以下であってもよい。 In the formula (1), X represents a base material, R 1 represents a divalent organic group, R 2 represents an alkyl group having 1 to 5 or 1 to 3 carbon atoms, and Ar 3 represents a phosphine oxide group. The attached arylene group (for example, a phenylene group, a biphenylene group, a naphthylene group) is shown. p represents an integer of 1 to 3 corresponding to the number of three oxygen atoms bonded to Si that are bonded to the base material X. * Indicates the portion of the phosphine oxide group bonded to the phosphorus atom. R 1 is usually an organic group derived from a synthetic pathway that induces a linker group. For example, R 1 may be a group containing an amide group, and an example of the linker group L in that case is represented by the following formula (1a). R 3 in the formula (1a) represents an alkylene group. The carbon number of the alkylene group as R 3 may be, for example, 1 or more or 2 or more, and may be 20 or less, 15 or less, or 10 or less.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（Ｉ）中のＡｒ１及びＡｒ２は、それぞれ独立に、置換基を有していてもよいアリール基を示す。Ａｒ１又はＡｒ２としてのアリール基は、芳香族化合物から１個の水素原子を除いた残基であることができる。アリール基の具体例としては、置換又は無置換のベンゼン、置換又は無置換のナフタレン、置換又は無置換のアントラセン、又は置換又は無置換のフェナントレンから１個の水素原子を除いた残基が挙げられる。特に、Ａｒ１及びＡｒ２が置換又は無置換のフェニル基であってもよい。アリール基が有する置換基は、ハロゲン原子であってもよい。 Ar 1 and Ar 2 in the formula (I) each independently represent an aryl group which may have a substituent. The aryl group as Ar 1 or Ar 2 can be a residue obtained by removing one hydrogen atom from an aromatic compound. Specific examples of aryl groups include substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, or substituted or unsubstituted phenanthrene with one hydrogen atom removed. .. In particular, Ar 1 and Ar 2 may be substituted or unsubstituted phenyl groups. The substituent contained in the aryl group may be a halogen atom.
　発光材料に導入される希土類錯体を構成する希土類イオンは、通常、三価の希土類イオンである。希土類イオンは、発光色等に応じて、適宜選択することができる。希土類イオンは、例えば、Ｅｕ（ＩＩＩ）イオン、Ｔｂ（ＩＩＩ）イオン、Ｇｄ（ＩＩＩ）イオン、Ｓｍ（ＩＩＩ）イオン、Ｙｂ（ＩＩＩ）イオン、Ｎｄ（ＩＩＩ）イオン、Ｅｒ（ＩＩＩ）イオン、Ｙ（ＩＩＩ）イオン、Ｄｙ（ＩＩＩ）イオン、Ｃｅ（ＩＩＩ）イオン、及びＰｒ（ＩＩＩ）イオンからなる群より選ばれる少なくとも一種であることができる。高い発光強度を得る観点から、希土類イオンは、Ｅｕ（ＩＩＩ）イオン、Ｔｂ（ＩＩＩ）イオン、Ｇｄ（ＩＩＩ）イオン又はこれらの組み合わせであってもよい。 The rare earth ion constituting the rare earth complex introduced into the luminescent material is usually a trivalent rare earth ion. Rare earth ions can be appropriately selected depending on the emission color and the like. Rare earth ions include, for example, Eu (III) ion, Tb (III) ion, Gd (III) ion, Sm (III) ion, Yb (III) ion, Nd (III) ion, Er (III) ion, Y ( It can be at least one selected from the group consisting of III) ions, Dy (III) ions, Ce (III) ions, and Pr (III) ions. From the viewpoint of obtaining high emission intensity, the rare earth ion may be Eu (III) ion, Tb (III) ion, Gd (III) ion or a combination thereof.
　式（Ｉ）として例示される発光材料は、希土類錯体と配位結合を形成している、リンカー基Ｌを有するホスフィンオキシド配位子以外のｎ座の配位子Ｚを更に有する。配位子Ｚは二座配位子であってもよく、その例としては下記式（２）で表されるジケトン配位子が挙げられる。ジケトン配位子は、光増感作用により希土類錯体の発光強度等の更なる向上に寄与することができる。 The luminescent material exemplified as the formula (I) further has an n-position ligand Z other than the phosphine oxide ligand having a linker group L, which forms a coordinate bond with the rare earth complex. The ligand Z may be a bidentate ligand, and examples thereof include a diketone ligand represented by the following formula (2). The diketone ligand can contribute to further improvement of the emission intensity and the like of the rare earth complex by the photosensitizing action.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式（２）中、Ｒ１１及びＲ１２は、それぞれ独立に置換基を有していてもよい脂肪族基又は置換基を有していてもよい芳香族基を示し、Ｒ１３は水素原子、置換基を有していてもよい脂肪族基又は置換基を有していてもよい芳香族基を示し、Ｒ１３がＲ１１又はＲ１２と結合して、置換基を有していてもよい環状基を形成していてもよい。Ｒ１３は重水素原子であってもよい。 In the formula (2), R 11 and R 12 represent an aliphatic group which may independently have a substituent or an aromatic group which may have a substituent, and R 13 is a hydrogen atom. It indicates an aliphatic group which may have a substituent or an aromatic group which may have a substituent, and R 13 may be bonded to R 11 or R 12 to have a substituent. It may form a cyclic group. R 13 may be a deuterium atom.
　Ｒ１１、Ｒ１２及びＲ１３は、それぞれ独立にアルキル基（例えば、メチル基、ｔｅｒｔ－ブチル基）、ハロゲン化アルキル基、アリール基又はハロゲン化アリール基であってもよい。アルキル基及びハロゲン化アルキル基の炭素数は１～１０であってもよい。Ｒ１１、Ｒ１２又はＲ１３としてのハロゲン化アルキル基は、炭素数１～５のフルオロアルキル基（例えばトリフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロブチル基、パーフルオロペンチル基）であってもよい。Ｒ１１、Ｒ１２又はＲ１３としてのアリール基は、フェニル基、ナフチル基、又はチエニル基であってもよく、これらがハロゲン化されていてもよい。 R 11 , R 12 and R 13 may each independently be an alkyl group (eg, a methyl group, a tert-butyl group), an alkyl halide group, an aryl group or an aryl halide group. The alkyl group and the halogenated alkyl group may have 1 to 10 carbon atoms. The alkyl halide group as R 11 , R 12 or R 13 is a fluoroalkyl group having 1 to 5 carbon atoms (for example, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl). It may be a group). The aryl group as R 11 , R 12 or R 13 may be a phenyl group, a naphthyl group, or a thienyl group, and these may be halogenated.
　Ｒ１３がＲ１１又はＲ１２と結合して形成される環状基は、置換基を有していてもよい環状の脂肪族基、芳香族基又はこれらの組み合わせからなる基であってもよい。 The cyclic group formed by binding R 13 to R 11 or R 12 may be a cyclic aliphatic group, an aromatic group, or a group consisting of a combination thereof, which may have a substituent.
　配位子Ｚが光学活性を有していてもよい。光学活性を有する配位子Ｚを発光材料に導入することにより、発光材料に円偏光特性が付与され得る。光学活性を有する配位子Ｚは、例えば、下記式（２０）で表されるカンファ―誘導体又はその鏡像異性体であってもよい。２種の鏡像異性体を任意の比率で組み合わせてもよい。 The ligand Z may have optical activity. By introducing the optically active ligand Z into the light emitting material, the light emitting material can be imparted with circularly polarized light characteristics. The optically active ligand Z may be, for example, a camphor derivative represented by the following formula (20) or an enantiomer thereof. The two enantiomers may be combined in any ratio.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式（２０）中、Ｒ２１は式（２）中のＲ１１と同義である。Ｒ２２、Ｒ２３及びＲ２４はそれぞれ独立に置換基を有していてもよい炭化水素基を示し、Ｒ２５、Ｒ２６、Ｒ２７及びＲ２８はそれぞれ独立に水素原子、ハロゲン原子、又は置換基を有していてもよい炭化水素基を示す。Ｒ２２、Ｒ２３及びＲ２４は置換基を有していてもよいアルキル基であってもよく、その炭素数は１～５であってもよい。Ｒ２２、Ｒ２３及びＲ２４の具体例としては、メチル基が挙げられる。Ｒ２５、Ｒ２６、Ｒ２７及びＲ２８はそれぞれ独立に置換されていてもよいアルキル基であってもよく、その炭素数は１～５であってもよい。Ｒ２５、Ｒ２６、Ｒ２７及びＲ２８が水素原子であってもよい。式（２０）で表されるカンファー誘導体及びその鏡像異性体の具体例としては、３－（トリフルオロアセチル）カンホラート（ｔｆｃ）、及び３－（パーフルオロブチリル）－（±）－カンホラートが挙げられる。 In equation (20), R 21 is synonymous with R 11 in equation (2). R 22 , R 23 and R 24 each represent a hydrocarbon group which may have a substituent independently, and R 25 , R 26 , R 27 and R 28 independently represent a hydrogen atom, a halogen atom, or a substituent, respectively. Indicates a hydrocarbon group which may have a group. R 22 , R 23 and R 24 may be an alkyl group which may have a substituent and may have 1 to 5 carbon atoms. Specific examples of R 22 , R 23 and R 24 include a methyl group. R 25 , R 26 , R 27 and R 28 may each be an independently substituted alkyl group and may have 1 to 5 carbon atoms. R 25 , R 26 , R 27 and R 28 may be hydrogen atoms. Specific examples of the camphor derivative represented by the formula (20) and its enantiomer include 3- (trifluoroacetyl) camphorate (tfc) and 3- (perfluorobutyryl)-(±) -camphorate. Be done.
　発光材料は、例えば、基材Ｘの金属酸化物又は金属硫化物と結合を形成する官能基（例えば加水分解性シリル基）を含むリンカー基、及び、ホスフィンオキシド基を含むホスフィンオキシド配位子を有する化合物を、基材Ｘに結合させる工程と、基材Ｘにリンカー基を介して結合したホスフィンオキシド配位子と希土類イオンとで希土類錯体を形成させる工程とを含む方法によって得ることができる。下記式（３）は、発光材料の製造に用いることのできる、加水分解性シリル基を含むリンカー基、及びホスフィンオキシド配位子を有する化合物の一例を示す。式（３）中のＲ１、Ｒ２、Ａｒ１、Ａｒ２及びＡｒ３は前記と同義である。 The luminescent material includes, for example, a linker group containing a functional group (for example, a hydrolyzable silyl group) forming a bond with the metal oxide or metal sulfide of the base material X, and a phosphine oxide ligand containing a phosphine oxide group. It can be obtained by a method including a step of binding the compound to the base material X and a step of forming a rare earth complex with a phosphine oxide ligand bonded to the base material X via a linker group and a rare earth ion. The following formula (3) shows an example of a compound having a linker group containing a hydrolyzable silyl group and a phosphine oxide ligand that can be used in the production of a light emitting material. R 1 , R 2 , Ar 1 , Ar 2 and Ar 3 in the formula (3) have the same meanings as described above.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式（３）の化合物は、例えば、下記式（１１）で表される、加水分解性シリル基及びアミノ基を有する化合物と、下記式（１２）で表される、ホスフィンオキシド基及びカルボキシル基を有する化合物又はその誘導体との反応により得ることができる。式（１１）及び（１２）のようにアミノ基及びカルボキシル基の反応に限られず、反応により化学結合を生成し得る官能基の組み合わせを含む化合物を任意に適用することができる。 The compound of the formula (3) includes, for example, a compound having a hydrolyzable silyl group and an amino group represented by the following formula (11), and a phosphine oxide group and a carboxyl group represented by the following formula (12). It can be obtained by reacting with a compound or a derivative thereof. Not limited to the reaction of an amino group and a carboxyl group as in the formulas (11) and (12), a compound containing a combination of functional groups capable of forming a chemical bond by the reaction can be arbitrarily applied.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　発光インクの一例は、粒子状の発光材料と、発光材料が分散した分散媒とを含むことができる。発光インクを用いた印刷法等により発光体の膜を形成することができる。分散媒は特に制限されないが、例えばメタノール、エタノール、水、アセトン、ヘキサン、クロロホルム、ジクロロメタン、ジエチルエーテル、酢酸エチル、ベンゼン、トルエン、又はこれらの組み合わせであってもよい。発光インクが、スチレン、アクリル酸、メタクリル酸、アクリル酸誘導体、メタクリル酸誘導体（メタクリル酸メチル、メタクリル酸エチルなど）、又はポリマー（ポリスチレン、ポリメタクリル酸メチルなど）を含んでもよい。 An example of the luminescent ink can include a particulate luminescent material and a dispersion medium in which the luminescent material is dispersed. A film of a light emitting body can be formed by a printing method using light emitting ink or the like. The dispersion medium is not particularly limited, but may be, for example, methanol, ethanol, water, acetone, hexane, chloroform, dichloromethane, diethyl ether, ethyl acetate, benzene, toluene, or a combination thereof. The luminescent ink may contain styrene, acrylic acid, methacrylic acid, acrylic acid derivatives, methacrylic acid derivatives (methyl methacrylate, ethyl methacrylate, etc.), or polymers (polystyrene, polymethyl methacrylate, etc.).
　発光体の一例は、上述の実施形態に係る発光材料を含む。この発光体は、各種の発光デバイス、又はセキュリティ材を構成することができる。発光デバイスの例としては、マイクロＬＥＤ、交通標識及び電飾看板のような表示装置、液晶バックライト、並びに照明ディスプレイが挙げられる。 An example of a light emitting body includes a light emitting material according to the above-described embodiment. This light emitting body can form various light emitting devices or security materials. Examples of light emitting devices include micro LEDs, display devices such as traffic signs and illuminated signs, liquid crystal backlights, and lighting displays.
　以下、実施例を挙げて本発明についてさらに具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
Ｉ．SiO2-Eu(hfa)3[TPPO-Si(O)3]2
１．合成
（１）Eu(hfa)3(H2O)2
　酢酸ユーロピウム　１水和物(0.87 g, 2 mmol)を10 mLを蒸留水に溶解させた。そこに、1,1,1,5,5,5-Hexafluoro-2,4-pentandinone(0.9 mL, 6 mmol)の溶液を滴下した。室温で４時間の撹拌し、析出した黄色粉体を濾別し、メタノール／水の混合溶媒から再結晶させた。得られた結晶をトルエンで洗浄し、真空下で乾燥して、Eu(hfa)3(H2O)2を得た(収量1.12 g, 収率69%）。
IR spectrum (cm-1): ν(C=O) 1647 (s), ν(C-F) 1251-1136 (s)cm-1
1H NMR (CD3OD, 400 MHz, 300K) δ, ppm: 3.90 (s, 3H, CF3CH); 19F NMR (CD3OD,376 MHz, 300 K) δ, ppm: -80.8 (s, CF3) ppm I. SiO 2 -Eu (hfa) 3 [TPPO-Si (O) 3 ] 2
1. 1. Synthesis (1) Eu (hfa) 3 (H 2 O) 2
10 mL of Europium acetate monohydrate (0.87 g, 2 mmol) was dissolved in distilled water. A solution of 1,1,1,5,5,5-Hexafluoro-2,4-pentandinone (0.9 mL, 6 mmol) was added dropwise thereto. The mixture was stirred at room temperature for 4 hours, and the precipitated yellow powder was filtered off and recrystallized from a mixed solvent of methanol / water. The obtained crystals were washed with toluene and dried under vacuum to obtain Eu (hfa) 3 (H 2 O) 2 (yield 1.12 g, yield 69%).
IR spectrum (cm -1 ): ν (C = O) 1647 (s), ν (CF) 1251-1136 (s) cm -1
1 H NMR (CD 3 OD, 400 MHz, 300 K) δ, ppm: 3.90 (s, 3H, CF 3 CH); 19 F NMR (CD 3 OD, 376 MHz, 300 K) δ, ppm: -80.8 (s) , CF 3 ) ppm
（２）４－（ジフェニルホスフィノ）安息香酸の合成
Figure JPOXMLDOC01-appb-C000008
 (2) Synthesis of 4- (diphenylphosphino) benzoic acid
Figure JPOXMLDOC01-appb-C000008
　ジフェニル（ｐ－トリル）ホスフィン(5.0 g)をシュレンク管に入れ、更にKMnO4(11.1 g)及びNaOH(0.43 M, 65 mL)を加えた。シュレンク管を９０℃で１５時間加熱し、高温の懸濁液をセライトを用いて濾過した。得られた溶液をジエチルエーテルで２回洗浄し、50% H2SO4を加えること固形分を析出させた。固形分を濾別し、エタノールから再結晶させた。回収された白色結晶をジエチルエーテルで洗浄し真空下で乾燥させて、４－（ジフェニルホスフィノ）安息香酸を得た（収量3.1 g, 収率55%）。
IR spectrum (cm-1): ν(COO) 1705(s) and 1251(s), ν(P=O)1155(s)
1H NMR (CD3OD, 400 MHz, 300K) δ (ppm): 8.16 (m, 2H, Ar); 7.76 (m, 2H, Ar); 7.67 (m, 6H, Ar); 7.58 (m, 4H,Ar). 31P NMR (CD3OD,162 MHz, 300K) δ (ppm) : 32.1 (s) Diphenyl (p-tolyl) phosphine (5.0 g) was placed in a Schlenk tube, and KMnO 4 (11.1 g) and NaOH (0.43 M, 65 mL) were further added. The Schlenk tube was heated at 90 ° C. for 15 hours and the hot suspension was filtered through Celite. The resulting solution was washed twice with diethyl ether and 50% H 2 SO 4 was added to precipitate solids. The solids were filtered off and recrystallized from ethanol. The recovered white crystals were washed with diethyl ether and dried under vacuum to give 4- (diphenylphosphino) benzoic acid (yield 3.1 g, yield 55%).
IR spectrum (cm -1 ): ν (COO) 1705 (s) and 1251 (s), ν (P = O) 1155 (s)
1 H NMR (CD 3 OD, 400 MHz, 300K) δ (ppm): 8.16 (m, 2H, Ar); 7.76 (m, 2H, Ar); 7.67 (m, 6H, Ar); 7.58 (m, 4H) , Ar). 31 P NMR (CD 3 OD, 162 MHz, 300K) δ (ppm): 32.1 (s)
（３）ホスフィンオキシド配位子TPPO-Si(OEt)3
Figure JPOXMLDOC01-appb-C000009
 (3) Phosphine oxide ligand TPPO-Si (OEt) 3
Figure JPOXMLDOC01-appb-C000009
　４－（ジフェニルホスフィノ）安息香酸(0.61 g, 1.95 mmol)をシュレンク管に入れ、窒素雰囲気下、塩化チオニル(12mL)を加えた。室温で２時間の反応の後、過剰の塩化チオニルを除去して、単黄色の固体を得た。この固体を乾燥アセトニトリル(10 mL)に溶解し、溶液にトリエチルアミン(2.16 mL, 15.34 mmol)及び３－アミノプロピルトリエトキシシラン(0.49 mL, 2.05 mmol)を加え、溶液を室温で１．５時間撹拌した。溶媒を除去し、固体を水に懸濁させ、塩化メチレンで抽出した。塩化メチレン層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥し、溶媒を除去して、暗褐色の粗生成物を得た。粗生成物を、酢酸エチルを溶出液として用いたシリカゲルカラムクロマトグラフィーによって精製して、TPPO-Si(OEt)3を得た（収量577 mg, 収率56%）。
Elemental analysis calcd for C28H36NO5PSi(525.66): C, 63.98; H, 6.90; N, 2.66; Found: C, 63.64; H, 6.97; N, 2.60
1H NMR (CD3OD, 400 MHz, 300K) δ (ppm): 7.94 (m, 2H, Ar), 7.54-7.78 (m, 12H, Ar) overlapping with (t, 1H, CO-NH),3.83 (t, 6H, CH2-O-Si), 3.38 (m, 2H, N-CH2CH2CH2-Si),1.72(t, 2H, -CH2-CH2-Si), 1.20 (t, 9H, CH3-CH2-O-),0.68 (t, 2H, -CH2-Si)
31P NMR (CDCl3,162 MHz, 300K) δ (ppm) : 32.1 (s) 4- (Diphenylphosphino) benzoic acid (0.61 g, 1.95 mmol) was placed in a Schlenk tube, and thionyl chloride (12 mL) was added under a nitrogen atmosphere. After 2 hours of reaction at room temperature, excess thionyl chloride was removed to give a monoyellow solid. This solid is dissolved in dry acetonitrile (10 mL), triethylamine (2.16 mL, 15.34 mmol) and 3-aminopropyltriethoxysilane (0.49 mL, 2.05 mmol) are added to the solution, and the solution is stirred at room temperature for 1.5 hours. did. The solvent was removed, the solid was suspended in water and extracted with methylene chloride. The methylene chloride layer was washed with saturated brine, dried over magnesium sulfate, and the solvent was removed to obtain a dark brown crude product. The crude product was purified by silica gel column chromatography using ethyl acetate as an eluent to obtain TPPO-Si (OEt) 3 (yield 577 mg, yield 56%).
Elemental analysis calcd for C 28 H 36 NO 5 PSi (525.66): C, 63.98; H, 6.90; N, 2.66; Found: C, 63.64; H, 6.97; N, 2.60
1 H NMR (CD 3 OD, 400 MHz, 300K) δ (ppm): 7.94 (m, 2H, Ar), 7.54-7.78 (m, 12H, Ar) overlapping with (t, 1H, CO-NH), 3.83 (t, 6H, CH 2 -O-Si), 3.38 (m, 2H, N-CH 2 CH 2 CH 2 -Si), 1.72 (t, 2H, -CH 2 -CH 2 -Si), 1.20 (t , 9H, CH 3 -CH 2 -O-), 0.68 (t, 2H, -CH 2 -Si)
31 P NMR (CDCl 3, 162 MHz, 300K) δ (ppm): 32.1 (s)
（４）Ｅｕ錯体（Eu(hfa)3[TPPO-Si(OEt)3]2）
Figure JPOXMLDOC01-appb-C000010
 (4) Eu complex (Eu (hfa) 3 [TPPO-Si (OEt) 3 ] 2 )
Figure JPOXMLDOC01-appb-C000010
　Eu(hfa)3(H2O)2を１×１０－３ｍｂａｒの減圧下、１３５℃で４時間加熱することにより脱水させた。脱水させたEu(hfa)3(H2O)2(90mg, 0.11 mmol)をシュレンク管に入れ、窒素雰囲気下、乾燥エタノール（10 mL)を加え、その後、TPPO-Si(OEt)3(115 mg. 0.22 mmol)を加えた。形成された黄色の溶液を室温で５時間撹拌した。続いて溶媒を除去し、生成物を真空下で乾燥させて、）Eu(hfa)3[TPPO-Si(OEt)3]2を得た（収量189 mg, 収率94%）。
Elemental analysis calcd (%) for C71H75EuF18N2O16P2Si2(1824.4): C, 46.74; H, 4.14; N, 1.54; Found: C, 46.59; H, 4.38; N, 1.53 Eu (hfa) 3 (H 2 O) 2 was dehydrated by heating at 135 ° C. for 4 hours under a reduced pressure of 1 × 10 -3 mbar. Dehydrated Eu (hfa) 3 (H 2 O) 2 (90 mg, 0.11 mmol) is placed in a Schlenk tube, dry ethanol (10 mL) is added under a nitrogen atmosphere, and then TPPO-Si (OEt) 3 (115 mL) is added. mg. 0.22 mmol) was added. The yellow solution formed was stirred at room temperature for 5 hours. Subsequently, the solvent was removed and the product was dried under vacuum to give) Eu (hfa) 3 [TPPO-Si (OEt) 3 ] 2 (yield 189 mg, 94% yield).
Elemental analysis calcd (%) for C 71 H 75 EuF 18 N 2 O 16 P 2 Si 2 (1824.4): C, 46.74; H, 4.14; N, 1.54; Found: C, 46.59; H, 4.38; N, 1.53
（５）シリカナノ粒子
　アンモニア溶液（28%, 9.5 mL)、トリエトキシシラン(7.0 mL)、及び無水エタノール(183 mL)を丸底フラスコに入れた。形成された溶液を４５℃で１晩撹拌して、シリカナノ粒子を含む乳白色の分散液を得た。４０００ｒｐｍの遠心分離によってシリカナノ粒子を回収し、無水エタノール(185mL)中に超音波法によって分散させた。 (5) Silica nanoparticles Ammonia solution (28%, 9.5 mL), triethoxysilane (7.0 mL), and absolute ethanol (183 mL) were placed in a round bottom flask. The formed solution was stirred at 45 ° C. overnight to obtain a milky white dispersion containing silica nanoparticles. Silica nanoparticles were recovered by centrifugation at 4000 rpm and dispersed in absolute ethanol (185 mL) by ultrasonic method.
（６）シリカナノ粒子に固定されたＥｕ錯体を有する発光材料（SiO2-Eu(hfa)3[TPPO-Si(O)3]2）
Figure JPOXMLDOC01-appb-C000011
 (6) Luminescent material having an Eu complex immobilized on silica nanoparticles (SiO 2- Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 )
Figure JPOXMLDOC01-appb-C000011
　シリカナノ粒子のエタノール分散液(6 mL)を丸底フラスコに入れ、そこに窒素雰囲気下、TPPO-Si(OEt)3(142mg, 0.270 mmol)を徐々に加え、混合液を室温で一晩撹拌した。次いで、脱水させたEu(hfa)3(H2O)2(109 mg, 0.135 mmol)を加え、形成された反応液を室温で１２時間撹拌した。シリカナノ粒子を遠心分離によって単離し、赤色の排出物が紫外光(365 nm)で観測されなくなるまでジエチルエーテルで洗浄した。洗浄後の粒子を真空下で乾燥させて、Ｅｕ錯体によって修飾された淡黄色のシリカナノ粒子（SiO2-Eu(hfa)3[TPPO-Si(O)3]2）を得た。 An ethanol dispersion (6 mL) of silica nanoparticles was placed in a round bottom flask, TPPO-Si (OEt) 3 (142 mg, 0.270 mmol) was gradually added thereto under a nitrogen atmosphere, and the mixture was stirred overnight at room temperature. .. Then, dehydrated Eu (hfa) 3 (H 2 O) 2 (109 mg, 0.135 mmol) was added, and the formed reaction solution was stirred at room temperature for 12 hours. Silica nanoparticles were isolated by centrifugation and washed with diethyl ether until no red emissions were observed in ultraviolet light (365 nm). The washed particles were dried under vacuum to obtain pale yellow silica nanoparticles (SiO 2- Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 ) modified by the Eu complex.
２．評価
（１）粒径
　Ｅｕ錯体による修飾前のシリカナノ粒子、及び、Ｅｕ錯体で修飾されたシリカナノ粒子である発光材料（SiO2-Eu(hfa)3[TPPO-Si(O)3]2）を動的光散乱法によって測定した。修飾前のシリカナノ粒子の平均粒径は３６ｎｍであり、粒子状の発光材料（SiO2-Eu(hfa)3[TPPO-Si(O)3]2）の平均粒径は５３ｎｍであった。 2. 2. Evaluation (1) Particle size Silica nanoparticles before modification with Eu complex and light-emitting materials (SiO 2- Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 ) which are silica nanoparticles modified with Eu complex. It was measured by the dynamic light scattering method. The average particle size of the silica nanoparticles before modification was 36 nm, and the average particle size of the particulate luminescent material (SiO 2- Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 ) was 53 nm.
（２）透過型電子顕微鏡（ＴＥＭ），エネルギー分散型Ｘ線分析（ＥＤＳ）
　修飾前のシリカナノ粒子、及び、Ｅｕ錯体で修飾されたシリカナノ粒子（SiO2-Eu(hfa)3[TPPO-Si(O)3]2）を透過型電子顕微鏡によって観察した。図１は修飾前のシリカナノ粒子の透過型電子顕微鏡写真であり、図２は、粒子状の発光材料（SiO2-Eu(hfa)3[TPPO-Si(O)3]2）の透過型電子顕微鏡写真である。SiO2-Eu(hfa)3[TPPO-Si(O)3]2の像において、Ｅｕ錯体に由来すると考えられる暗領域が多数観察された。さらに、SiO2-Eu(hfa)3[TPPO-Si(O)3]2の像をエネルギー分散型Ｘ線分析（ＥＤＳ）によって分析したところ、Ｅｕ、Ｐ、Ｆ、Ｓｉ、Ｃ及びＯの存在が確認され、このことからもＥｕ錯体がシリカナノ粒子上に導入されたことが示唆された。図３は、SiO2-Eu(hfa)3[TPPO-Si(O)3]2のＥＤＳスペクトルである。 (2) Transmission electron microscope (TEM), energy dispersive X-ray analysis (EDS)
The unmodified silica nanoparticles and the silica nanoparticles modified with the Eu complex (SiO 2- Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 ) were observed with a transmission electron microscope. FIG. 1 is a transmission electron micrograph of unmodified silica nanoparticles, and FIG. 2 shows transmission electrons of a particulate luminescent material (SiO 2- Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 ). It is a micrograph. In the image of SiO 2- Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 , many dark regions considered to be derived from the Eu complex were observed. Furthermore, when the image of SiO 2 -Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 was analyzed by energy dispersive X-ray analysis (EDS), the presence of Eu, P, F, Si, C and O was obtained. Was confirmed, and this also suggested that the Eu complex was introduced onto the silica nanoparticles. FIG. 3 is an EDS spectrum of SiO 2- Eu (hfa) 3 [TPPO-Si (O) 3 ] 2.
（３）フーリエ変換赤外分光（ＦＴ－ＩＲ）
　図４は、TPPO-Si(OEt)3、Eu(hfa)3[TPPO-Si(OEt)3]2、及びSiO2-Eu(hfa)3[TPPO-Si(O)3]2のＦＴ－ＩＲスペクトルである。Eu(hfa)3(TPPO)2及びEu(hfa)3[TPPO-Si(OEt)3]2のＦＴ－ＩＲスペクトルにおいて、TPPO-Si(OEt)3の場合に観測されたＰ＝Ｏ伸縮に由来する１１８４ｃｍ－１のシグナルは観測されず、１１４２ｃｍ－１のシグナルが観測され、このようなシグナルのシフトから、Ｐ＝Ｏ基とＥｕ（ＩＩＩ）との配位結合の形成が示唆された。 (3) Fourier Transform Infrared Spectroscopy (FT-IR)
Figure 4 shows the FT- of TPPO-Si (OEt) 3 , Eu (hfa) 3 [TPPO-Si (OEt) 3 ] 2 , and SiO 2- Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 . IR spectrum. In the FT-IR spectra of Eu (hfa) 3 (TPPO) 2 and Eu (hfa) 3 [TPPO-Si (OEt) 3 ] 2 , the P = O expansion and contraction observed in the case of TPPO-Si (OEt) 3 No 1184 cm -1 signal was observed, but a 1142 cm -1 signal was observed, suggesting the formation of a coordinate bond between the P = O group and Eu (III) from such a signal shift.
（４）熱重量分析
　熱重量分析により、Eu(hfa)3[TPPO-Si(OEt)3]2及びSiO2-Eu(hfa)3[TPPO-Si(O)3]2の分解温度がそれぞれ２０８℃及び３０６℃であることが確認された。 (4) Thermogravimetric analysis By thermogravimetric analysis, the decomposition temperatures of Eu (hfa) 3 [TPPO-Si (OEt) 3 ] 2 and SiO 2 -Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 are respectively. It was confirmed that the temperature was 208 ° C and 306 ° C.
（５）光物理的特性
　図５は、固体状態のEu(hfa)3(H2O)2、Eu(hfa)3[TPPO-Si(OEt)3]2、及びSiO2-Eu(hfa)3[TPPO-Si(O)3]2の励起スペクトルである。Eu(hfa)3[TPPO-Si(OEt)3]2、及びSiO2-Eu(hfa)3[TPPO-Si(O)3]2の励起スペクトルでは、３０４ｎｍ及び３３４ｎｍにおいてπ－π＊遷移に起因する幅広い吸収が観測された。 (5) Photophysical properties Fig. 5 shows Eu (hfa) 3 (H 2 O) 2 , Eu (hfa) 3 [TPPO-Si (OEt) 3 ] 2 , and SiO 2 -Eu (hfa) in the solid state. 3 [TPPO-Si (O) 3 ] 2 is the excitation spectrum. In the excitation spectra of Eu (hfa) 3 [TPPO-Si (OEt) 3 ] 2 and SiO 2- Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 , there is a π-π * transition at 304 nm and 334 nm. Widespread absorption due to it was observed.
　図６は、固体状態のEu(hfa)3(H2O)2、Eu(hfa)3[TPPO-Si(OEt)3]2、及びSiO2-Eu(hfa)3[TPPO-Si(O)3]2の発光スペクトル（励起光：３５６ｎｍ）である。SiO2-Eu(hfa)3[TPPO-Si(O)3]2は、Eu(hfa)3(H2O)2、及びEu(hfa)3[TPPO-Si(OEt)3]2と比較して顕著に強い発光を示した。 FIG. 6 shows Eu (hfa) 3 (H 2 O) 2 , Eu (hfa) 3 [TPPO-Si (OEt) 3 ] 2 , and SiO 2 -Eu (hfa) 3 [TPPO-Si (O) in the solid state. ) 3 ] 2 emission spectrum (excitation light: 356 nm). SiO 2 -Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 compared to Eu (hfa) 3 (H 2 O) 2 and Eu (hfa) 3 [TPPO-Si (OEt) 3 ] 2. It showed a remarkably strong luminescence.
　図７は、固体状態のEu(hfa)3(H2O)2、Eu(hfa)3[TPPO-Si(OEt)3]2、及びSiO2-Eu(hfa)3[TPPO-Si(O)3]2、並びに溶液中でのEu(hfa)3[TPPO-Si(OEt)3]2の発光減衰を示すグラフである。SiO2-Eu(hfa)3[TPPO-Si(O)3]2は、Eu(hfa)3(H2O)2、及びEu(hfa)3[TPPO-Si(OEt)3]2と比較して長い発光寿命を示した。表１に各Ｅｕ錯体の光物理的特性（発光寿命τｏｂｓ、放射速度定数ｋｒ、無放射速度定数ｋｎｒ、４ｆ－４ｆ遷移の発光量子効率Φｆ－ｆ及びトータルの発光量子収率Φｔｏｔ）を示す。SiO2-Eu(hfa)3[TPPO-Si(O)3]2は比較的大きなｋｒを示し、小さなｋｎｒを示した。SiO2-Eu(hfa)3[TPPO-Si(O)3]2は、２つ以上のリンカー基を用いた基材Ｘ上への希土類錯体の固定化によって、基材Ｘ上に希土類錯体が安定的に固定化することで、放射速度増大と熱失活過程の抑制が可能となり高い発光量子効率を示すと考えられる。 Figure 7 shows Eu (hfa) 3 (H 2 O) 2 , Eu (hfa) 3 [TPPO-Si (OEt) 3 ] 2 , and SiO 2 -Eu (hfa) 3 [TPPO-Si (O) in the solid state. ) 3 ] 2 , and a graph showing the emission attenuation of Eu (hfa) 3 [TPPO-Si (OEt) 3 ] 2 in solution. SiO 2 -Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 compared to Eu (hfa) 3 (H 2 O) 2 and Eu (hfa) 3 [TPPO-Si (OEt) 3 ] 2. It showed a long emission life. Table 1 shows the photophysical characteristics of each Eu complex (emission lifetime τ obs, radiation rate constant k r , non-radiation rate constant k nr , emission quantum efficiency Φ ff of 4f-4f transition, and total emission quantum yield Φ. tot ) is shown. SiO 2- Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 showed a relatively large kr and a small knr. SiO 2- Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 has a rare earth complex on the base material X due to immobilization of the rare earth complex on the base material X using two or more linker groups. It is considered that stable immobilization makes it possible to increase the radiation velocity and suppress the heat deactivation process, and to show high emission quantum efficiency.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
ＩＩ．SiO2-Gd(hfa)3[TPPO-Si(O)3]2
１．合成
（１）Ｇｄ錯体（Gd(hfa)3[TPPO-Si(OEt)3]2）
　Eu(hfa)3(H2O)2に代えてGd(hfa)3(H2O)2を用いたこと以外はEu(hfa)3[TPPO-Si(OEt)3]2の合成と同様の手順で、Ｇｄ錯体（Gd(hfa)3[TPPO-Si(OEt)3]2）を合成した。
（２）シリカナノ粒子に固定されたＥｕ錯体を有する発光材料（SiO2-Gd(hfa)3[TPPO-Si(O)3]2）
　Eu(hfa)3(H2O)2に代えてGd(hfa)3(H2O)2を用いたこと以外はSiO2-Eu(hfa)3[TPPO-Si(O)3]2）の合成と同様の手順で、Ｇｄ錯体によって修飾されたシリカナノ粒子（SiO2-Gd(hfa)3[TPPO-Si(O)3]2）を合成した。 II. SiO 2 -Gd (hfa) 3 [TPPO-Si (O) 3 ] 2
1. 1. Synthesis (1) Gd complex (Gd (hfa) 3 [TPPO-Si (OEt) 3 ] 2 )
Similar to the synthesis of Eu (hfa) 3 [TPPO-Si (OEt) 3 ] 2 except that Gd (hfa) 3 (H 2 O) 2 was used instead of Eu (hfa) 3 (H 2 O) 2. Gd complex (Gd (hfa) 3 [TPPO-Si (OEt) 3 ] 2 ) was synthesized by the procedure of.
(2) Luminescent material having an Eu complex immobilized on silica nanoparticles (SiO 2- Gd (hfa) 3 [TPPO-Si (O) 3 ] 2 )
SiO 2- Eu (hfa) 3 [TPPO-Si (O) 3 ] 2 ) except that Gd (hfa) 3 (H 2 O) 2 was used instead of Eu (hfa) 3 (H 2 O) 2. Silica nanoparticles modified with a Gd complex (SiO 2- Gd (hfa) 3 [TPPO-Si (O) 3 ] 2 ) were synthesized by the same procedure as in the synthesis of.
２．評価
　Gd(hfa)3[TPPO-Si(OEt)3]2、及びSiO2-Gd(hfa)3[TPPO-Si(O)3]2の固体状態での温度９０Ｋにおける発光寿命τｏｂｓ（励起光：３５６ｎｍ）を測定した。Gd(hfa)3[TPPO-Si(OEt)3]2の発光寿命は４７ｍｓで、SiO2-Gd(hfa)3[TPPO-Si(O)3]2の発光寿命は１５ｍｓであった。 2. 2. Evaluation Gd (hfa) 3 [TPPO-Si (OEt) 3 ] 2 and SiO 2 -Gd (hfa) 3 [TPPO-Si (O) 3 ] 2 Emission lifetime at 90 K in solid state τ obs (excitation) Light: 356 nm) was measured. The emission lifetime of Gd (hfa) 3 [TPPO-Si (OEt) 3 ] 2 was 47 ms, and the emission lifetime of SiO 2- Gd (hfa) 3 [TPPO-Si (O) 3 ] 2 was 15 ms.
ＩＩＩ．SiO2-Eu(tfc)3[TPPO-Si(O)3]2
１．合成
（１）Eu(tfc)3(H2O)2
　酢酸ユーロピウム　１水和物(200 mg, 0.61 mmol)を50 mLを蒸留水に溶解させた。そこに、アンモニア水を数滴滴下した後、(+)-3-(Trifluoroacetyl)camphor(463 mg, 1.83 mmol)のメタノール(15 mL)溶液を加えて。室温で４時間の撹拌し、析出した黄色粉体を濾別し、メタノール／水の混合溶媒から再結晶させた。得られた結晶を真空下で乾燥して、Eu(tfc)3(H2O)2を得た(収量346 mg, 収率61%）。
19F NMR (CD3OD, 376 MHz, 300 K) δ, ppm: -79.64 (s, CF3) ppm.
Elemental analysis calcd (%) for C36H46EuF9O8 (929.7): C, 46.51%, H, 4.99%; Found: C, 46.45%, H, 4.91% III. SiO 2 -Eu (tfc) 3 [TPPO-Si (O) 3 ] 2
1. 1. Synthesis (1) Eu (tfc) 3 (H 2 O) 2
50 mL of Europium acetate monohydrate (200 mg, 0.61 mmol) was dissolved in distilled water. After dropping a few drops of aqueous ammonia, a solution of (+)-3- (Trifluoroacetyl) camphor (463 mg, 1.83 mmol) in methanol (15 mL) was added thereto. The mixture was stirred at room temperature for 4 hours, and the precipitated yellow powder was filtered off and recrystallized from a mixed solvent of methanol / water. The obtained crystals were dried under vacuum to obtain Eu (tfc) 3 (H 2 O) 2 (yield 346 mg, yield 61%).
19 F NMR (CD 3 OD, 376 MHz, 300 K) δ, ppm: -79.64 (s, CF 3 ) ppm.
Elemental analysis calcd (%) for C 36 H 46 EuF 9 O 8 (929.7): C, 46.51%, H, 4.99%; Found: C, 46.45%, H, 4.91%
（２）Ｅｕ錯体（Eu(tfc)3[TPPO-Si(OEt)3]2）
Figure JPOXMLDOC01-appb-C000013
 　Eu(hfa)3(H2O)2に代えてEu(tfc)3(H2O)2を用いたこと以外はEu(hfa)3[TPPO-Si(OEt)3]2の合成と同様の手順で、Ｅｕ錯体（Eu(tfc)3[TPPO-Si(OEt)3]2）を合成した。
（３）シリカナノ粒子に固定されたＥｕ錯体を有する発光材料（SiO2-Eu(tfc)3[TPPO-Si(O)3]2）
　Eu(hfa)3(H2O)2に代えてEu(tfc)3(H2O)2を用いたこと以外はSiO2-Eu(hfa)3[TPPO-Si(O)3]2）の合成と同様の手順で、Ｇｄ錯体によって修飾された淡黄色のシリカナノ粒子（SiO2-Eu(tfc)3[TPPO-Si(O)3]2）を得た。 (2) Eu complex (Eu (tfc) 3 [TPPO-Si (OEt) 3 ] 2 )
Figure JPOXMLDOC01-appb-C000013
 Eu (hfa) 3 (H 2 O) 2 in place of Eu (tfc) 3 (H 2 O) except that 2 using Eu (hfa) 3 similar to the [TPPO-Si (OEt) 3 ] 2 Synthesis Eu complex (Eu (tfc) 3 [TPPO-Si (OEt) 3 ] 2 ) was synthesized by the procedure of.
(3) Luminescent material having an Eu complex immobilized on silica nanoparticles (SiO 2- Eu (tfc) 3 [TPPO-Si (O) 3 ] 2 )
Eu (hfa) 3 (H 2 O) 2 in place of Eu (tfc) 3 (H 2 O) except that 2 with SiO 2 -Eu (hfa) 3 [ TPPO-Si (O) 3] 2) The pale yellow silica nanoparticles modified with the Gd complex (SiO 2- Eu (tfc) 3 [TPPO-Si (O) 3 ] 2 ) were obtained by the same procedure as the synthesis of.
２．評価
　Eu(tfc)3(H2O)2、Eu(tfc)3[TPPO-Si(OEt)3]2、及びSiO2-Eu(tfc)3[TPPO-Si(O)3]2の固体状態での光物理的特性を測定した。表２に各Ｅｕ錯体の光物理的特性（発光寿命τｏｂｓ、放射速度定数ｋｒ、無放射速度定数ｋｎｒ、４ｆ－４ｆ遷移の発光量子効率Φｆ－ｆ及びトータルの発光量子収率Φｔｏｔ）を示す。SiO2-Eu(tfc)3[TPPO-Si(O)3]2は、Eu(tfc)3(H2O)2、Eu(tfc)3[TPPO-Si(OEt)3]2と比較して長い発光寿命及び高い発光量子収率を示した。
Figure JPOXMLDOC01-appb-T000014
 2. 2. Evaluation Eu (tfc) 3 (H 2 O) 2 , Eu (tfc) 3 [TPPO-Si (OEt) 3 ] 2 , and SiO 2 -Eu (tfc) 3 [TPPO-Si (O) 3 ] 2 solids The photophysical properties in the state were measured. Table 2 shows the photophysical characteristics of each Eu complex (emission lifetime τ obs, radiation rate constant k r , non-radiation rate constant k nr , emission quantum efficiency Φ ff of 4f-4f transition, and total emission quantum yield Φ. tot ) is shown. SiO 2 -Eu (tfc) 3 [TPPO-Si (O) 3 ] 2 is compared with Eu (tfc) 3 (H 2 O) 2 , Eu (tfc) 3 [TPPO-Si (OEt) 3 ] 2. It showed a long emission lifetime and a high emission quantum yield.
Figure JPOXMLDOC01-appb-T000014

Claims (9)

  1. 　金属酸化物又は金属硫化物のうち少なくとも一方を含む基材と、
    　前記基材に結合した２以上のリンカー基と、
    　ぞれぞれの前記リンカー基に結合した、１つのホスフィンオキシド基を有するホスフィンオキシド配位子と、
    　希土類イオンと、
    を含み、
    　１つの前記希土類イオンと２以上の前記ホスフィンオキシド配位子とで希土類錯体が形成されている、
    発光材料。     A substrate containing at least one of a metal oxide or a metal sulfide,
    Two or more linker groups bonded to the substrate and
    A phosphine oxide ligand having one phosphine oxide group bonded to each of the above linker groups,
    Rare earth ions and
    Including
    A rare earth complex is formed by one of the rare earth ions and two or more of the phosphine oxide ligands.
    Luminescent material.
  2. 　前記リンカー基が加水分解性シリル基の残基及びアリーレン基を含む、請求項１に記載の発光材料。 The luminescent material according to claim 1, wherein the linker group contains a residue of a hydrolyzable silyl group and an arylene group.
  3. 　前記基材が二酸化ケイ素を含む、請求項１又は２に記載の発光材料。 The light emitting material according to claim 1 or 2, wherein the base material contains silicon dioxide.
  4. 　当該発光材料が、前記希土類イオンと配位結合を形成している、光学活性を有する配位子を更に含む、請求項１～３のいずれか一項に記載の発光材料。 The luminescent material according to any one of claims 1 to 3, further comprising an optically active ligand in which the luminescent material forms a coordinate bond with the rare earth ion.
  5. 　前記基材が粒子である、請求項１～４のいずれか一項に記載の発光材料。 The light emitting material according to any one of claims 1 to 4, wherein the base material is particles.
  6. 　前記基材が平均粒径１００ｎｍ以下の粒子である、請求項１～４のいずれか一項に記載の発光材料。 The light emitting material according to any one of claims 1 to 4, wherein the substrate is particles having an average particle size of 100 nm or less.
  7. 　請求項５又は６に記載の発光材料と、前記発光材料が分散した分散媒と、を含む、発光インク。 A luminescent ink comprising the luminescent material according to claim 5 or 6 and a dispersion medium in which the luminescent material is dispersed.
  8. 　請求項１～６のいずれか一項に記載の発光材料を含む発光体。 A luminescent material containing the luminescent material according to any one of claims 1 to 6.
  9. 　請求項８に記載の発光体を備える発光デバイス。 A light emitting device comprising the light emitting body according to claim 8.
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