JP5849255B2 - Circularly polarized light-emitting rare earth complex - Google Patents
Circularly polarized light-emitting rare earth complex Download PDFInfo
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- JP5849255B2 JP5849255B2 JP2011269916A JP2011269916A JP5849255B2 JP 5849255 B2 JP5849255 B2 JP 5849255B2 JP 2011269916 A JP2011269916 A JP 2011269916A JP 2011269916 A JP2011269916 A JP 2011269916A JP 5849255 B2 JP5849255 B2 JP 5849255B2
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Description
本発明は、円偏光発光性を示す希土類錯体、並びにそれを利用した光学機能材料及びセキュリティー技術に関する。 The present invention relates to a rare earth complex exhibiting circularly polarized light emission, an optical functional material and security technology using the same.
近年、円偏光発光性を示す光学機能材料を有機ＥＬ素子と組み合わせることにより、光学機能材料を３次元表示ディスプレイや電子ペーパーに応用することが期待されている。また、円偏光発光性を示す光学機能材料は、通常の可視光の中に右円偏光及び左円偏光をセキュリティー情報として付与することができることから、セキュリティーマーカーや不可視性インキの原料としても注目を集めている。 In recent years, it is expected that an optical functional material is applied to a three-dimensional display or electronic paper by combining an optical functional material exhibiting circularly polarized light emission with an organic EL element. In addition, optically functional materials that exhibit circularly polarized light emission can be given security information such as right circularly polarized light and left circularly polarized light in normal visible light. Collecting.
このような光学機能材料の一つに希土類錯体がある。例えば、BINAPOをはじめとするビナフチル構造配位子と、facam（3-trifluoroacetyl-D-camphorate）誘導体の両方が希土類イオンに配位した希土類錯体、TPPOをはじめとするホスフィンオキシド誘導体とfacam誘導体の両方が希土類イオンに配位した希土類錯体が報告されている（特許文献１〜３）。これらの希土類錯体は、ビナフチル構造配位子やホスフィンオキシド誘導体のジアステレオマー構造に由来する不斉配位子場により、右円偏光及び左円偏光を選択的に発光する、即ち円偏光発光性を有することが分かっている。一方、４個のhfbc（3-hepatafluoro-butylryl-(+)-camphorate）が希土類イオンに配位した希土類錯体や、不斉配位子場環境下における希土類錯体が、円偏光発光性を示すことが報告されている（非特許文献１及び２）。これらの希土類錯体は８配位の構造となっている。また、不斉ビスオキサゾリンピリジン骨格配位子とアセチルアセトン誘導体が配位した希土類錯体が報告されているが（特許文献４）、この希土類錯体は９配位の構造となっている。希土類錯体は、一般に８配位又は９配位の構造をとることが多い。 One such optical functional material is a rare earth complex. For example, both binaphthyl ligands such as BINAPO and rare earth complexes in which both facam (3-trifluoroacetyl-D-camphorate) derivatives are coordinated to rare earth ions, both phosphine oxide derivatives such as TPPO and facam derivatives Have been reported (Patent Documents 1 to 3). These rare earth complexes selectively emit right and left circularly polarized light by the asymmetric ligand field derived from the diastereomeric structure of binaphthyl structure ligands and phosphine oxide derivatives, that is, circularly polarized light emission. Is known to have On the other hand, rare earth complexes in which four hfbc (3-hepatafluoro-butylryl-(+)-camphorate) coordinate to rare earth ions and rare earth complexes in an asymmetric ligand field environment exhibit circularly polarized light emission. Have been reported (Non-Patent Documents 1 and 2). These rare earth complexes have an 8-coordinate structure. Further, a rare earth complex in which an asymmetric bisoxazoline pyridine skeleton ligand and an acetylacetone derivative are coordinated has been reported (Patent Document 4), and this rare earth complex has a nine-coordinate structure. Rare earth complexes generally have an 8-coordinate or 9-coordinate structure.
分子の円偏光発光性はｇ値（異方性因子）で示すことができる。ｇ値は次のように定義される値である。
CDスペクトルからのｇ値＝Δε／ε＝２（εＬ−εＲ）/（εＬ＋εＲ）
（式中、εＬは左円偏光における吸収係数、εＲは右円偏光における吸収係数を表す。）
CPLスペクトルからのｇ値＝ΔＩ／Ｉ＝２（ＩＬ−ＩＲ）/（ＩＬ＋ＩＲ）
（式中、ＩＬは左回りの円偏光発光強度、ＩＲは右回りの円偏光発光強度を表す。）
なお、ｇ値をCDスペクトルから求める場合及びCPLスペクトルから求める場合のいずれにおいても、理論上、ｇ値の最大絶対値は２である。
The circularly polarized light-emitting property of a molecule can be represented by a g value (anisotropic factor). The g value is a value defined as follows.
G value from CD spectrum = Δε / ε = 2 (εL−εR) / (εL + εR)
(In the formula, εL represents an absorption coefficient in left circularly polarized light, and εR represents an absorption coefficient in right circularly polarized light.)
G value from CPL spectrum = ΔI / I = 2 (IL−IR) / (IL + IR)
(In the formula, IL represents counterclockwise circularly polarized light emission intensity, and IR represents clockwise circularly polarized light emission intensity.)
Note that the maximum absolute value of the g value is 2 theoretically in both cases where the g value is obtained from the CD spectrum and the CPL spectrum.
従来の有機化合物のCPLスペクトルにおけるｇ値は0.001程度である。これに対して、ビナフチル構造配位子とfacam誘導体の両方が配位した希土類錯体のｇ値は0.01程度であり、ホスフィンオキシド誘導体とfacam誘導体の両方が配位した希土類錯体のｇ値は0.44であることが報告されている。なお、希土類錯体が示すｇ値の世界最大値は約1.3である（非特許文献１参照）。
従って、これら希土類錯体のｇ値は従来の有機化合物のｇ値に比較すると格段に高く、円偏光発光性に優れているといえる。
The g value in the CPL spectrum of a conventional organic compound is about 0.001. In contrast, the g value of the rare earth complex coordinated by both the binaphthyl structure ligand and the facam derivative is about 0.01, and the g value of the rare earth complex coordinated by both the phosphine oxide derivative and the facam derivative is 0.44. It has been reported. In addition, the world largest value of g value which a rare earth complex shows is about 1.3 (refer nonpatent literature 1).
Accordingly, the g value of these rare earth complexes is much higher than that of conventional organic compounds, and it can be said that the rare earth complex is excellent in circularly polarized light emission.
しかしながら、希土類錯体と偏光板等を組み合わせたセキュリティー技術に応用する上では、上記した程度のｇ値では未だ不十分であって、より高い円偏光発光性を有する新規希土類錯体の開発が望まれていた。 However, the g value of the above degree is still insufficient for application to security technology combining a rare earth complex and a polarizing plate, and development of a new rare earth complex having higher circularly polarized light emission is desired. It was.
本発明は上記課題を解決するために成されたものであり、本発明の目的は、より高い円偏光発光性を有する希土類錯体を提供することにある。また、本発明の目的は、セキュリティー技術分野について十分に応用可能な円偏光発光性を有する希土類錯体、並びにそれを利用した光学機能材料及びセキュリティー技術を提供することにある。 The present invention has been made to solve the above problems, and an object of the present invention is to provide a rare earth complex having higher circularly polarized light emission. Another object of the present invention is to provide a rare earth complex having a circularly polarized light emission property that can be sufficiently applied in the field of security technology, an optical functional material using the rare earth complex, and a security technology.
本発明者らは、鋭意研究を重ねた結果、希土類錯体は配位数によって異なる円偏光発光性を示すことを見出し、８配位型の希土類錯体よりも高い円偏光発光性を示す７配位型の希土類錯体を得るに至った。
本明細書では、円偏光発光性を有する希土類錯体を円偏光発光性希土類錯体と呼ぶ。
As a result of intensive studies, the present inventors have found that rare earth complexes exhibit circularly polarized light emission that varies depending on the coordination number, and 7-coordinated light that exhibits higher circularly polarized light emission than 8-coordinated rare earth complexes. The type of rare earth complex has been obtained.
In this specification, a rare earth complex having circularly polarized light emission is referred to as a circularly polarized light emitting rare earth complex.
本発明に係る円偏光発光性希土類錯体は、７配位型の円偏光発光性希土類錯体であって、
一般式（１）
で表され、
Ｒ３は二座の不斉なアセチルアセトン配位子であって、
一般式（２）
で表され、
Ｒ１に含まれるＮ原子、Ｏ原子のいずれかと、Ｒ２に結合しているＰ原子が結合し、前記Ｎ原子、Ｏ原子のいずれかと前記Ｐ原子を含む４〜６員環の環構造が形成されていることを特徴とする。
The circularly polarized light-emitting rare earth complex according to the present invention is a seven-coordinate circularly polarized light-emitting rare earth complex,
General formula (1)
Represented by
R3 is a bidentate asymmetric acetylacetone ligand,
General formula (2)
Represented by
Either the N atom or O atom contained in R1 and the P atom bonded to R2 are bonded to form a 4- to 6-membered ring structure containing either the N atom or O atom and the P atom. It is characterized by.
上記した７配位型の円偏光発光性希土類錯体は、
一般式（８）
で表され、
Ｒ３は二座の不斉なアセチルアセトン配位子であって、
一般式（２）
で表されることを特徴とする、８配位型の円偏光発光性希土類錯体と互変異性の関係にある。
The seven-coordinate circularly polarized light-emitting rare earth complex described above is
General formula (8)
Represented by
R3 is a bidentate asymmetric acetylacetone ligand,
General formula (2)
It has a tautomeric relationship with an 8-coordinate type circularly polarized light-emitting rare earth complex characterized by the following.
本発明によれば、従来の希土類錯体が示すことのなかった、極めて高い円偏光発光性を有する円偏光発光性希土類錯体を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the circularly polarized light emitting rare earth complex which has the extremely high circularly polarized light emission property which the conventional rare earth complex did not show can be provided.
まず、本発明に係る７配位型の円偏光発光性希土類錯体の構造的特徴について説明する。
本発明に係る７配位型の円偏光発光性希土類錯体は、
一般式（１）
で表され、
Ｒ３は二座の不斉なアセチルアセトン配位子であって、
一般式（２）
で表され、
Ｒ１に含まれるＮ原子、Ｏ原子のいずれかと、Ｒ２に結合しているＰ原子が結合し、前記Ｎ原子、Ｏ原子のいずれかと前記Ｐ原子を含む４〜６員環の環構造が形成されていることを特徴としている。
First, the structural features of the seven-coordinate circularly polarized light-emitting rare earth complex according to the present invention will be described.
The seven-coordinate circularly polarized light-emitting rare earth complex according to the present invention is
General formula (1)
Represented by
R3 is a bidentate asymmetric acetylacetone ligand,
General formula (2)
Represented by
Either the N atom or O atom contained in R1 and the P atom bonded to R2 are bonded to form a 4- to 6-membered ring structure containing either the N atom or O atom and the P atom. It is characterized by having.
なお、Ｒ３は不斉な配位子であることから、Ｌ１〜Ｌ３が全て同じである場合、Ｌ１及びＬ３が同じである場合は除く。 In addition, since R3 is an asymmetric ligand, when L1 to L3 are all the same, the case where L1 and L3 are the same is excluded.
さらに具体的には、本発明に係る７配位型の円偏光発光性希土類錯体は、
一般式（３）
で表され、
Ａ１〜Ａ４は同一又は異なる炭素数３〜２０の炭素芳香族炭化水素基、複素芳香族化合物基または炭化水素基
のいずれかで表すことができる。
More specifically, the seven-coordinate circularly polarized light-emitting rare earth complex according to the present invention is:
General formula (3)
Represented by
A1 to A4 can be represented by any of the same or different carbon aromatic hydrocarbon groups having 3 to 20 carbon atoms, heteroaromatic compound groups, or hydrocarbon groups.
本発明に係る７配位型の円偏光発光性希土類錯体の大きな特徴は、ジホスフィンオキシド配位子が単座の配位子として希土類イオンと結合している点にある。従来、ジホスフィンオキシド配位子は、二座の配位子として希土類イオンと結合する例しか知られていなかった。しかし、本発明では、ジホスフィンオキシド配位子が二座の配位子として希土類イオンに結合する８配位型の円偏光発光性希土類錯体を互変異性化することにより、７配位型の円偏光発光性希土類錯体を得ることを見出した。 A major feature of the seven-coordinate circularly polarized light-emitting rare earth complex according to the present invention is that a diphosphine oxide ligand is bonded to a rare earth ion as a monodentate ligand. Conventionally, diphosphine oxide ligands have only been known to bind to rare earth ions as bidentate ligands. However, in the present invention, a seven-coordinate type circularly polarized light-emitting rare earth complex in which a diphosphine oxide ligand binds to a rare earth ion as a bidentate ligand is tautomerized. It has been found that a polarized luminescent rare earth complex is obtained.
即ち、本発明に係る８配位型の円偏光発光性希土類錯体は、本発明に係る７配位型の円偏光発光性希土類錯体の互変異性体であって、二座のジホスフィンオキシド配位子１個と、二座の不斉なアセチルアセトン配位子３個を、希土類イオンに配位させたものである。
本発明に係る８配位型の円偏光発光性希土類錯体は、
一般式（８）
で表され、
Ｒ３は二座の不斉なアセチルアセトン配位子であって、
一般式（２）
で表すことができる。
That is, the eight-coordinate circularly polarized light-emitting rare earth complex according to the present invention is a tautomer of the seven-coordinated circularly polarized light-emitting rare earth complex according to the present invention, and has a bidentate diphosphine oxide coordination. One element and three bidentate asymmetric acetylacetone ligands are coordinated to a rare earth ion.
The 8-coordinate circularly polarized light-emitting rare earth complex according to the present invention is:
General formula (8)
Represented by
R3 is a bidentate asymmetric acetylacetone ligand,
General formula (2)
Can be expressed as
さらに具体的には、本発明に係る８配位型の円偏光発光性希土類錯体は、
一般式（９）
で表され、
Ａ１〜Ａ４は同一又は異なる炭素数３〜２０の炭素芳香族炭化水素基、複素芳香族化合物基または炭化水素基
のいずれかで表すことができる。
More specifically, the 8-coordinate circularly polarized light-emitting rare earth complex according to the present invention is:
General formula (9)
Represented by
A1 to A4 can be represented by any of the same or different carbon aromatic hydrocarbon groups having 3 to 20 carbon atoms, heteroaromatic compound groups, or hydrocarbon groups.
次に、本発明に係る７配位型及び８配位型の円偏光発光性希土類錯体が共通して有する構造上の特徴について以下に述べる。
本発明に係るこれらの円偏光発光性希土類錯体が有する、二座の不斉なアセチルアセトン配位子は、不斉性と光増感機能の双方を有する。不斉な配位子は、希土類錯体の円偏光発光性を向上させる。
Next, structural features common to the seven-coordinate and eight-coordinate circularly polarized light-emitting rare earth complexes according to the present invention will be described below.
The bidentate asymmetric acetylacetone ligands possessed by these circularly polarized light-emitting rare earth complexes according to the present invention have both asymmetry and a photosensitization function. The asymmetric ligand improves the circularly polarized light emission property of the rare earth complex.
特に、上記アセチルアセトン配位子として、
一般式（６）
で表されるカンファー誘導体を用いることにより、より高い光増感機能を有する円偏光発光性希土類錯体を得ることができる。
上記アセチルアセトン配位子としてのカンファー誘導体は、ハロゲン化炭素誘導体であることが好ましく、炭素数１から６のハロゲン化炭素誘導体など、例えば炭素数１から３の直鎖フッ化炭素が挙げられる。
ここでは、Ｚ２及びＺ３と異なり、Ｚ１には水素原子又は重水素原子が適用されない。その理由は、希土類イオンと結合するＯ原子と直接結合するＣ原子がＣ−Ｈ単結合を有すると、Ｃ−Ｈ単結合の振動性によって円偏光発光性希土類錯体の発光性が低下するためである。
また、アセチルアセトン配位子としてカンファー誘導体のような嵩高い分子を採用することにより、希土類イオンの周辺に物理的な障壁が生じ、円偏光発光性希土類錯体の分子同士が架橋して配位高分子になることを防ぐことができる。
In particular, as the acetylacetone ligand,
General formula (6)
By using the camphor derivative represented by the following formula, a circularly polarized light-emitting rare earth complex having a higher photosensitization function can be obtained.
The camphor derivative as the acetylacetone ligand is preferably a halogenated carbon derivative, such as a halogenated carbon derivative having 1 to 6 carbon atoms, such as a linear fluorocarbon having 1 to 3 carbon atoms.
Here, unlike Z2 and Z3, no hydrogen atom or deuterium atom is applied to Z1. The reason is that when the C atom directly bonded to the O atom bonded to the rare earth ion has a C—H single bond, the light emission of the circularly polarized light emitting rare earth complex is lowered due to the vibration of the C—H single bond. is there.
Also, by adopting bulky molecules such as camphor derivatives as acetylacetone ligands, a physical barrier is created around the rare earth ions, and the molecules of the circularly polarized light-emitting rare earth complex are cross-linked with each other to form a coordination polymer. Can be prevented.
さらに、本発明に係る円偏光発光性希土類錯体が共通して有する、ジホスフィンオキシド配位子は、二個のＰ＝Ｏ基を有する。Ｐ＝Ｏ基の二重結合は低振動型構造として知られており、このような構造を有する配位子が配位することにより、本発明に係る円偏光発光性希土類錯体の発光性を向上させることができる。
上記ジホスフィンオキシド配位子において、Ｐ原子に結合するＡ１〜Ａ４は、同一又は異なる
一般式（４−１）〜（４−３）
のいずれかで表されるように、Ｐ原子に結合するＣ原子がＣ−Ｈ単結合を有しないことが好ましい。これは、Ｃ−Ｈ単結合の振動性によって円偏光発光性希土類錯体の発光性が低下することを防ぐためである。さらに、Ａ１〜Ａ４として、３〜２０個の炭素を含む嵩高い分子を用いることが好ましい。例えば芳香族炭化水素基、複素芳香族化合物基、炭化水素基など、好ましくはフェニル基やｔ−ブチル基またはｎ−ブチル基などの嵩高い分子が挙げられる。
Furthermore, the diphosphine oxide ligand that the circularly polarized light-emitting rare earth complex according to the present invention has in common has two P═O groups. The double bond of the P = O group is known as a low vibration type structure, and the light emission of the circularly polarized light-emitting rare earth complex according to the present invention is improved by coordination of a ligand having such a structure. Can be made.
In the diphosphine oxide ligand, A1 to A4 bonded to the P atom are the same or different. General formulas (4-1) to (4-3)
As represented by any of the above, it is preferable that the C atom bonded to the P atom does not have a C—H single bond. This is to prevent the light-emitting property of the circularly polarized light-emitting rare earth complex from being lowered by the vibrational property of the C—H single bond. Furthermore, it is preferable to use a bulky molecule containing 3 to 20 carbons as A1 to A4. For example, an aromatic hydrocarbon group, a heteroaromatic compound group, a hydrocarbon group, etc., preferably a bulky molecule such as a phenyl group, a t-butyl group or an n-butyl group.
こうした構造的な特徴を有することにより、本発明に係る７配位型の円偏光発光性希土類錯体及び８配位型の円偏光発光性希土類錯体は、高い円偏光発光性だけでなく、高い発光強度を示す。とりわけ、７配位型の円偏光発光性希土類錯体は、ジホスフィンオキシド配位子が単座の配位子として希土類イオンに結合することによって高い不斉性を有しており、そのために極めて高い円偏光発光性を示す。そのｇ値は、後述する実施例にて述べるように、希土類錯体が示すｇ値の世界最大値である約1.3（非特許文献１参照）を大幅に上回る。 By having such a structural feature, the seven-coordinate circularly polarized light-emitting rare earth complex and the eight-coordinated circularly polarized light-emitting rare earth complex according to the present invention have not only high circularly polarized light emission but also high light emission. Indicates strength. In particular, the seven-coordinate circularly polarized light-emitting rare earth complex has high asymmetry due to bonding of the diphosphine oxide ligand to the rare earth ion as a monodentate ligand, and thus extremely high circularly polarized light. Shows luminous properties. The g value greatly exceeds about 1.3 (see Non-Patent Document 1), which is the world's largest g value exhibited by the rare earth complex, as will be described later in Examples.
さらに、上記８配位型の円偏光発光性希土類錯体から７配位型の円偏光発光性希土類錯体を得る方法、及びそのメカニズムについて以下に説明する。 Further, a method for obtaining a seven-coordinate circularly polarized light-emitting rare earth complex from the above eight-coordinated circularly polarized light-emitting rare earth complex and its mechanism will be described below.
上述したように、本発明に係る７配位型の円偏光発光性希土類錯体及び８配位型の円偏光発光性希土類錯体は互変異性体の関係にある。これらの円偏光発光性希土類錯体を得るには、まず有機合成によって８配位型の円偏光発光性希土類錯体を作製後、これを所定の溶媒に溶解させることにより、７配位型の円偏光発光性希土類錯体に変化させる。その後、気化等によって溶媒を除去しても、円偏光発光性希土類錯体の配位型は変化しない。 As described above, the 7-coordinate circularly polarized light-emitting rare earth complex and the 8-coordinated circularly polarized light-emitting rare earth complex according to the present invention are in a tautomeric relationship. In order to obtain these circularly polarized light-emitting rare earth complexes, first, an 8-coordinate type circularly polarized light-emitting rare earth complex is prepared by organic synthesis, and then dissolved in a predetermined solvent to obtain a 7-coordinated type circularly polarized light complex. Change to luminescent rare earth complex. Thereafter, even if the solvent is removed by vaporization or the like, the coordination type of the circularly polarized light-emitting rare earth complex does not change.
より具体的には、本発明に係る８配位型の円偏光発光性希土類錯体をケトン系溶媒に溶解すると、配位子であるジホスフィンオキシド配位子において、該配位子と希土類イオンとの２つの結合のうちの一方が切断される。そして、例えば
一般式（１）
で表されるように、結合が切断された側のＰ＝Ｏ基のＯ原子が、結合が切断されない側のＰ原子と結合している共役複素環内のＮ原子又はＯ原子と結合し、４〜６員環の環構造が形成される。このように、二座のジホスフィンオキシド配位子が二座から単座となることによって、７配位型の円偏光発光性希土類錯体が得られる。このメカニズムは以下のように推測される。
More specifically, when the eight-coordinate circularly polarized light-emitting rare earth complex according to the present invention is dissolved in a ketone solvent, the diphosphine oxide ligand, which is the ligand, One of the two bonds is broken. For example, the general formula (1)
As shown below, the O atom of the P═O group on the side where the bond is broken is bonded to the N atom or the O atom in the conjugated heterocyclic ring bonded to the P atom on the side where the bond is not broken, A 4- to 6-membered ring structure is formed. Thus, a bidentate diphosphine oxide ligand is converted from a bidentate to a monodentate, whereby a seven-coordinate circularly polarized light-emitting rare earth complex is obtained. This mechanism is presumed as follows.
一般的にケトン基のＯ原子は配位結合性を有し、その結合エネルギーはＰ＝Ｏ基のＯ原子が有する配位結合性よりも大きいといわれている。８配位型の円偏光発光性希土類錯体をケトン系溶媒に溶解すると、溶媒分子中のケトン基のＯ原子が希土類イオンに作用することによって、Ｐ＝Ｏ基のＯ原子の配位結合の一方が切断される。配位結合が切断された側のＰ＝Ｏ基は、希土類イオンから遠ざかる。そして、このＰ＝Ｏ基のＯ原子と、配位結合を維持する側のＰ原子と結合している共役複素環内のＮ原子又はＯ原子の間に相互作用が働き、両者は結合する。その結果、Ｐ原子、及び、共役複素環内のＮ原子又はＯ原子を含む環構造がジホスフィンオキシド配位子内に形成される。こうした環構造が形成されることにより、ジホスフィンオキシド配位子は単座の配位子となる。
本発明に係る円偏光発光性希土類錯体では、複素環として、平面系の構造を有し、嵩高くなく、且つ自由回転の可能な共役複素環を導入することにより、このような環構造の形成が容易に生じるようにしている。
In general, an O atom of a ketone group has a coordination bond, and the bond energy is said to be larger than the coordination bond of an O atom of a P═O group. When an 8-coordinate type circularly polarized light-emitting rare earth complex is dissolved in a ketone solvent, the O atom of the ketone group in the solvent molecule acts on the rare earth ion, thereby causing one of the coordination bonds of the O atom of the P = O group. Is disconnected. The P═O group on the side where the coordination bond is cut away from the rare earth ions. Then, an interaction acts between the O atom of the P═O group and the N atom or O atom in the conjugated heterocyclic ring bonded to the P atom on the side maintaining the coordination bond, and both are bonded. As a result, a ring structure containing P atoms and N or O atoms in the conjugated heterocycle is formed in the diphosphine oxide ligand. By forming such a ring structure, the diphosphine oxide ligand becomes a monodentate ligand.
In the circularly polarized light-emitting rare earth complex according to the present invention, such a ring structure is formed by introducing a conjugated heterocycle having a planar structure as a heterocycle, not bulky, and capable of free rotation. Is easily generated.
また、以下のようなメカニズムも推測することができる。
本発明の円偏光発光性希土類錯体は、非ケトン系溶媒中において、８配位型として安定的に存在する。この８配位型の円偏光発光性希土類錯体は、ケトン系溶液中においては、溶媒の触媒作用により錯体構造が７配位型の構造へと変化すると考えられる。ここでいう触媒作用とは、ケトン系溶液中が活性化状態において中心金属イオンに配位することで８配位型から７配位構造型への構造変化反応の活性化障壁を下げることを意味している。一方で、ケトン系溶媒以外の非配位性溶媒においてはこのような触媒作用が得られないため、円偏光発光性希土類錯体が８配位型として安定的に存在するものと考えられる。
Moreover, the following mechanisms can also be estimated.
The circularly polarized light-emitting rare earth complex of the present invention stably exists as an 8-coordinate type in a non-ketone solvent. This octacoordinate circularly polarized light-emitting rare earth complex is considered to change its complex structure to a 7-coordinate structure in the ketone solution due to the catalytic action of the solvent. The catalytic action here means that the activation barrier of the structural change reaction from the 8-coordinate type to the 7-coordinated structure type is lowered by coordination with the central metal ion in the activated state in the ketone solution. doing. On the other hand, since such a catalytic action cannot be obtained in a non-coordinating solvent other than the ketone solvent, it is considered that the circularly polarized light-emitting rare earth complex exists stably as an 8-coordinate type.
なお、上記ケトン系溶媒は、
一般式（１２）
で表される鎖状又は環状のケトン系溶媒であることが望ましい。
The ketone solvent is
Formula (12)
A linear or cyclic ketone solvent represented by
逆に、７配位型の円偏光発光性希土類錯体を非ケトン系溶媒に溶解すると、８配位型の円偏光発光性希土類錯体へと変化する。
このような非ケトン系溶媒として、アセトニトリル、メトキシアセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル系溶媒、又は、ジクロロメタン、クロロホルム、四塩化炭素、ジクロロエタン、トリクロロエチレン等のハロゲン系溶媒を使用することができる。
Conversely, when a 7-coordinate circularly polarized light-emitting rare earth complex is dissolved in a non-ketone solvent, it changes to an 8-coordinated circularly polarized light-emitting rare earth complex.
As such non-ketone solvents, nitrile solvents such as acetonitrile, methoxyacetonitrile, propionitrile, and benzonitrile, or halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, and trichloroethylene can be used. .
また、ケトン系溶媒と非ケトン系溶媒を０：１０〜１０：０の割合で混合した析出溶媒を調製し、本発明に係る７配位型の円偏光発光性希土類錯体又は８配位型の円偏光発光性希土類錯体又はこれらの混合物を溶解させ、前記析出溶媒を気化等によって除去することにより、７配位型の円偏光発光性希土類錯体及び８配位型の円偏光発光性希土類錯体を所望の比率で含む円偏光発光性希土類錯体群を得ることができる。
このようにして得られた円偏光発光性希土類錯体群は、７配位型及び８配位型の円偏光発光性希土類錯体が単独で示す円偏光発光性、又はその存在比率に対応した円偏光発光性を示す。
以下、本発明に係る円偏光発光性希土類錯体（以下、「Ln(III)錯体」という）の具体的な実施例について述べる。
In addition, a precipitation solvent in which a ketone solvent and a non-ketone solvent are mixed at a ratio of 0:10 to 10: 0 is prepared, and the seven-coordinate circularly polarized light-emitting rare earth complex or the eight-coordinate type of the present invention is used. By dissolving a circularly polarized light-emitting rare earth complex or a mixture thereof and removing the precipitation solvent by vaporization or the like, a 7-coordinate circularly polarized light-emitting rare earth complex and an 8-coordinated circularly polarized light-emitting rare earth complex are obtained. A group of circularly polarized light-emitting rare earth complexes containing a desired ratio can be obtained.
The circularly polarized light-emitting rare earth complex group thus obtained is a circularly polarized light corresponding to the circularly polarized light emitting property or the abundance ratio of the seven-coordinate and eight-coordinated circularly polarized light-emitting rare earth complexes alone. Shows luminous properties.
Specific examples of the circularly polarized light-emitting rare earth complex according to the present invention (hereinafter referred to as “Ln (III) complex”) will be described below.
１．Ln(III)錯体の合成
図１（１）及び（２）に示す合成手順に従い、希土類イオンとしてEu(III)イオンを有するLn(III)錯体を合成した。図１及び以下の説明では、Meはメチル基、Phはフェニル基を示す。
まず、酢酸ユウロピウムn水和物（658mg、2.0mmol）および蒸留水150mLを500mLナスフラスコに加え、酢酸ユウロピウムn水和物が溶解するまで超音波処理を施し、酢酸ユウロピウム水溶液を得た。L-facam（1120mg、4.5mmol）をメタノール30mLに溶かし、前記酢酸ユウロピウム水溶液に撹拌しながら加え、室温で12時間撹拌した。生成した黄色の沈殿を吸引ろ過により回収した後、蒸留水で洗浄し、得られた黄色の粉末を減圧下で乾燥させた。これにより、[Eu(L-facam)3(H2O)2]を得た（図１（１））。[Eu(L-facam)3(H2O)2]の収量は1.183gであり、収率は85％であった。
1. Synthesis of Ln (III) Complex An Ln (III) complex having Eu (III) ions as rare earth ions was synthesized according to the synthesis procedure shown in FIGS. 1 (1) and (2). In FIG. 1 and the following description, Me represents a methyl group and Ph represents a phenyl group.
First, europium acetate n hydrate (658 mg, 2.0 mmol) and 150 mL of distilled water were added to a 500 mL eggplant flask and subjected to sonication until europium acetate n hydrate was dissolved to obtain a europium acetate aqueous solution. L-facam (1120 mg, 4.5 mmol) was dissolved in 30 mL of methanol, added to the above europium acetate aqueous solution with stirring, and stirred at room temperature for 12 hours. The produced yellow precipitate was collected by suction filtration, washed with distilled water, and the resulting yellow powder was dried under reduced pressure. Thereby, [Eu (L-facam) 3 (H 2 O) 2 ] was obtained (FIG. 1 (1)). The yield of [Eu (L-facam) 3 (H 2 O) 2 ] was 1.183 g, and the yield was 85%.
次に、得られた[Eu(L-facam)3(H2O)2]（930mg、1.0mmol）、BIPYPO（558mg、1.0mmol）及びメタノール100mLを200mlナスフラスコに入れ、70℃で15時間撹拌した。撹拌後、減圧下で溶媒を留去し、淡黄色の固体を得た。得られた淡黄色の固体をヘキサンに溶解させ、不溶物をろ過により取り除いた後、減圧下でろ液から溶媒を留去し、淡黄色の固体を得た。これにより、[Eu(BIPYPO)(L-facam)3]を得た（図１（２））。[Eu(BIPYPO)(L-facam)3]の収量は1.325gであり、収率は91%であった。 Next, the obtained [Eu (L-facam) 3 (H 2 O) 2 ] (930 mg, 1.0 mmol), BIPYPO (558 mg, 1.0 mmol) and 100 mL of methanol were placed in a 200 ml eggplant flask and stirred at 70 ° C. for 15 hours. Stir. After stirring, the solvent was distilled off under reduced pressure to obtain a pale yellow solid. The obtained pale yellow solid was dissolved in hexane, insoluble matters were removed by filtration, and then the solvent was distilled off from the filtrate under reduced pressure to obtain a pale yellow solid. As a result, [Eu (BIPYPO) (L-facam) 3 ] was obtained (FIG. 1 (2)). The yield of [Eu (BIPYPO) (L-facam) 3 ] was 1.325 g, and the yield was 91%.
さらに、得られた[Eu(BIPYPO)(L-facam)3]約100mgを少量のアセトンに溶解し、その溶液が濁るまでヘキサンを加え、濁りが消えるまで加熱した後、室温で静置して結晶を析出させた。以下の説明では、この結晶を結晶（Ａ）と呼ぶ。
また、得られた[Eu(BIPYPO)(L-facam)3]約100mgをアセトニトリル約5mlに溶解し、その溶液が濁るまでヘキサンを加え、濁りが消えるまで加熱した後、室温で静置して結晶を析出させた。以下の説明では、この結晶を結晶（Ｂ）と呼ぶ。
Further, about 100 mg of the obtained [Eu (BIPYPO) (L-facam) 3 ] was dissolved in a small amount of acetone, hexane was added until the solution became cloudy, and the mixture was heated until the cloudiness disappeared, and then allowed to stand at room temperature. Crystals were precipitated. In the following description, this crystal is referred to as crystal (A).
Also, dissolve about 100 mg of the obtained [Eu (BIPYPO) (L-facam) 3 ] in about 5 ml of acetonitrile, add hexane until the solution becomes cloudy, heat until the cloudiness disappears, and leave it at room temperature. Crystals were precipitated. In the following description, this crystal is referred to as crystal (B).
２．Ln(III)錯体の同定
得られた結晶（Ａ）及び結晶（Ｂ）をESI-MASS（エレクトロスプレー質量分析）及びＸ線結晶構造解析で同定した。ESI-MASSは日本電子株式会社（JEOL）製のJMS-700、MStationを用いた。また、Ｘ線結晶構造解析には株式会社リガク製の有機低分子Ｘ線構造解析装置（Rapid）を用いた。
ESI-MASSの結果を以下に示す。
2. Identification of Ln (III) Complex The obtained crystals (A) and (B) were identified by ESI- MASS (electrospray mass spectrometry) and X-ray crystal structure analysis. ESI-MASS used JMS-700 and MStation manufactured by JEOL Ltd. (JEOL). For the X-ray crystal structure analysis, an organic low molecular X-ray structure analyzer (Rapid) manufactured by Rigaku Corporation was used.
The results of ESI-MASS are shown below.
(1) 結晶（Ａ）
ESI-MASS(m/z)：[M-(facam)]+ calcd. for C58H54Eu1F6N2O6P2 +, 1201.25597、found, 1201.25605
(2) 結晶（Ｂ）
ESI-MASS(m/z)：[M-(facam]+ calcd. for C58H54Eu1F6N2O6P2 +, 1201.25597、found, 1201.25612
(1) Crystal (A)
ESI-MASS (m / z): [M- (facam)] + calcd. For C 58 H 54 Eu 1 F 6 N 2 O 6 P 2 + , 1201.25597, found, 1201.25605
(2) Crystal (B)
ESI-MASS (m / z): [M- (facam] + calcd. For C 58 H 54 Eu 1 F 6 N 2 O 6 P 2 + , 1201.25597, found, 1201.25612
また、結晶（Ａ）及び結晶（Ｂ）のＸ線結晶構造解析の結果を図２Ａ及び図２Ｂに示す。
ESI-MASSの結果及びＸ線結晶構造解析の結果から、得られた結晶（Ａ）は図３Ａに示す７配位型のEu(III)錯体であり、結晶（Ｂ）は図３Ｂに示す８配位型のEu(III)錯体であるといえる。この結果より、本実施例に係るEu(III)錯体は、溶媒条件によって配位数が変化することが示された。図２Ｂの、右端の２本の短い構造体は、結晶中に存在する溶媒のアセトニトリルである。このような溶媒は、いわゆる結晶水のように、結晶の錯体間の隙間を埋めるように存在し、必ずしも錯体の構造にかかわらないものである。
Moreover, the result of the X-ray crystal structure analysis of the crystal (A) and the crystal (B) is shown in FIGS. 2A and 2B.
From the results of ESI-MASS and X-ray crystal structure analysis, the obtained crystal (A) is a seven-coordinate Eu (III) complex shown in FIG. 3A, and the crystal (B) is shown in FIG. It can be said that it is a coordination type Eu (III) complex. From this result, it was shown that the coordination number of the Eu (III) complex according to this example varies depending on the solvent conditions. The two short structures at the right end of FIG. 2B are the solvent acetonitrile present in the crystals. Such a solvent exists like a so-called crystal water so as to fill a gap between crystal complexes, and is not necessarily concerned with the structure of the complex.
そこで、[Eu(BIPYPO)(L-facam)3]7.25mgを以下に示す溶媒5mLに溶解し、1mMのEu(III)錯体溶液（Ｃ）〜（Ｈ）を作製して、各種試験に供した。
Eu(III)錯体溶液（Ｃ）：アセトン（又は重アセトン-d6）
Eu(III)錯体溶液（Ｄ）：メチルエチルケトン
Eu(III)錯体溶液（Ｅ）：ジエチルケトン
Eu(III)錯体溶液（Ｆ）：シクロヘキサノン
Eu(III)錯体溶液（Ｇ）：アセトニトリル（又は重アセトニトリル-d3）
Eu(III)錯体溶液（Ｈ）：ジメチルスルホキシド（又は重ジメチルスルホキシド-d6）
Accordingly, 7.25 mg of [Eu (BIPYPO) (L-facam) 3 ] is dissolved in 5 mL of the solvent shown below to prepare 1 mM Eu (III) complex solutions (C) to (H), which are used for various tests. did.
Eu (III) complex solution (C): acetone (or heavy acetone-d6)
Eu (III) complex solution (D): methyl ethyl ketone
Eu (III) complex solution (E): diethyl ketone
Eu (III) complex solution (F): cyclohexanone
Eu (III) complex solution (G): acetonitrile (or deuterated acetonitrile-d3)
Eu (III) complex solution (H): dimethyl sulfoxide (or heavy dimethyl sulfoxide-d6)
３．Eu(III)錯体溶液の発光スペクトル
各Eu(III)錯体溶液（Ｃ）〜（Ｈ）の発光スペクトルを測定した。発光スペクトルの測定にはJASCOの分光蛍光光度計（FP-6500）を用いた。発光スペクトルの測定は、各Eu(III)錯体溶液（Ｃ）〜（Ｈ）について、溶存酸素による消光を防ぐためにArバブリングを10分間行った後に行った。励起波長は365nmに設定した。Eu(III)錯体溶液（Ｃ）〜（Ｈ）の発光スペクトルを図４に示す。
図４に示すように、いずれのEu(III)錯体溶液においても波長610〜620nm付近において高い発光強度が観察された。また、特にEu(III)錯体溶液（Ｃ）において最も高い発光強度が観察された。
3. Emission spectrum of Eu (III) complex solution The emission spectrum of each Eu (III) complex solution (C)-(H) was measured. A JASCO spectrofluorometer (FP-6500) was used to measure the emission spectrum. The emission spectrum was measured after Ar bubbling was performed for each Eu (III) complex solution (C) to (H) for 10 minutes in order to prevent quenching by dissolved oxygen. The excitation wavelength was set at 365 nm. The emission spectra of Eu (III) complex solutions (C) to (H) are shown in FIG.
As shown in FIG. 4, high emission intensity was observed in the vicinity of the wavelength of 610 to 620 nm in any Eu (III) complex solution. In addition, the highest emission intensity was observed particularly in the Eu (III) complex solution (C).
４．Eu(III)錯体溶液の円偏光発光性
Eu(III)錯体溶液（Ｃ）〜（Ｈ）の円偏光発光性を求めるために、Eu(III)錯体溶液（Ｃ）〜（Ｈ）のCPLスペクトルを測定した。代表としてEu(III)錯体溶液（Ｃ）のCPLスペクトルを図５に示す。
得られたCPLスペクトルの結果を基に、以下の式を用いてｇ値（gCD）を計算した。
CPLスペクトルからのｇ値＝ΔＩ／Ｉ＝２（ＩＬ−ＩＲ）/（ＩＬ＋ＩＲ）
（式中、ＩＬは左回りの円偏光発光強度、ＩＲは右回りの円偏光発光強度を表す。）
ｇ値の計算結果を以下に示す。
4). Circularly polarized light emission of Eu (III) complex solution
In order to obtain circularly polarized light emission properties of Eu (III) complex solutions (C) to (H), CPL spectra of Eu (III) complex solutions (C) to (H) were measured. As a representative, the CPL spectrum of the Eu (III) complex solution (C) is shown in FIG.
Based on the result of the obtained CPL spectrum, g value (gCD) was calculated using the following formula.
G value from CPL spectrum = ΔI / I = 2 (IL−IR) / (IL + IR)
(In the formula, IL represents counterclockwise circularly polarized light emission intensity, and IR represents clockwise circularly polarized light emission intensity.)
The calculation result of g value is shown below.
Eu(III)錯体溶液（Ｃ）：-1.81
Eu(III)錯体溶液（Ｄ）：-1.82
Eu(III)錯体溶液（Ｅ）：-0.41
Eu(III)錯体溶液（Ｆ）：-2.45
Eu(III)錯体溶液（Ｇ）：-0.66
Eu (III) complex solution (C): -1.81
Eu (III) complex solution (D):-1.82
Eu (III) complex solution (E): -0.41
Eu (III) complex solution (F): -2.45
Eu (III) complex solution (G): -0.66
このように、溶媒としてアセトンを用いたEu(III)錯体溶液（Ｃ）、（Ｄ）、（Ｆ）では、絶対値1.8を上回る極めて大きなｇ値が観察された。一方、アセトニトリルを用いたEu(III)錯体溶液（Ｇ）では、ケトン系溶媒を用いた他のEu(III)錯体溶液に比べて小さなｇ値が観察された。溶媒としてジメチルスルホキシドを用いたEu(III)錯体溶液（Ｈ）については、測定中にサンプルの退色が観察されたため、ｇ値を算出していない。
なお、ジエチルケトンを用いたEu(III)錯体溶液（Ｅ）が、他のケトン系溶媒を用いた溶液に比べて低いｇ値を示しているが、これは、ジエチルケトンの立体障害が大きく、Euイオンに配位しにくいためと考えられる。また、Eu(III)錯体溶液（Ｆ）のｇ値が理論値である２を超えているが、これは、当該溶液では左右円偏光のうち左円偏光の強度が極めて低く、そのためベースラインのノイズが左円偏光の強度に含まれているためと考えられる。
次に、本実施例に係るEu(III)錯体が示すｇ値の溶媒依存性について、以下に検証した。
Thus, in the Eu (III) complex solutions (C), (D), and (F) using acetone as a solvent, an extremely large g value exceeding the absolute value 1.8 was observed. On the other hand, in the Eu (III) complex solution (G) using acetonitrile, a small g value was observed as compared with other Eu (III) complex solutions using a ketone solvent. For Eu (III) complex solution (H) using dimethyl sulfoxide as a solvent, since the fading of the sample was observed during the measurement, the g value was not calculated.
In addition, Eu (III) complex solution (E) using diethyl ketone shows a lower g value than solutions using other ketone solvents, but this is because the steric hindrance of diethyl ketone is large, This is probably because it is difficult to coordinate to Eu ions. In addition, the g value of the Eu (III) complex solution (F) exceeds the theoretical value of 2, which is that the intensity of the left circularly polarized light is extremely low in the left and right circularly polarized light, and therefore the baseline This is probably because noise is included in the intensity of the left circularly polarized light.
Next, the solvent dependence of the g value exhibited by the Eu (III) complex according to this example was verified as follows.
５．Eu(III)錯体溶液のｇ値の溶媒依存性
[Eu(BIPYPO)(L-facam)3]の1mM重アセトン溶液及び1mM重アセトニトリルをそれぞれ調製し、両溶液を適宜混合して、重アセトン：重アセトニトリル＝100：0、63：37、35：65、0：100の計４種類の溶液を用意した。それぞれの溶液についてCPLスペクトルを測定し、ｇ値を得た。その結果を図６に示す。
図６に示されるように、アセトン100%において-1.81という大きな絶対値のｇ値が示された。また、ｇ値の絶対値は、アセトンの比率が下がるにつれて（即ち、アセトニトリルの比率が上がるにつれて）小さくなる傾向が認められ、アセトン0%（即ちアセトニトリル100%）では-0.66であった。
5. Solvent dependence of g value of Eu (III) complex solution
A 1 mM heavy acetone solution and 1 mM heavy acetonitrile of [Eu (BIPYPO) (L-facam) 3 ] are prepared, and both solutions are mixed as appropriate. Heavy acetone: heavy acetonitrile = 100: 0, 63:37, 35: A total of four solutions of 65, 0: 100 were prepared. The CPL spectrum was measured for each solution to obtain the g value. The result is shown in FIG.
As shown in FIG. 6, a large absolute g value of -1.81 was shown in 100% acetone. Further, the absolute value of the g value tended to decrease as the acetone ratio decreased (that is, as the acetonitrile ratio increased), and was −0.66 at 0% acetone (that is, 100% acetonitrile).
１．[Eu(BIPYPO)(D-facam)3]の合成
上述した実施例１における[Eu(BIPYPO)(L-facam)3]と同様の方法により、[Eu(BIPYPO)(D-facam)3]を合成した。[Eu(BIPYPO)(L-facam)3]及び[Eu(BIPYPO)(D-facam)3]について、以下に述べる通り円偏光発光性を調べた。
1. Synthesis of [Eu (BIPYPO) (D-facam) 3 ] By the same method as [Eu (BIPYPO) (L-facam) 3 ] in Example 1 described above, [Eu (BIPYPO) (D-facam) 3 ] Was synthesized. [Eu (BIPYPO) (L-facam) 3 ] and [Eu (BIPYPO) (D-facam) 3 ] were examined for circularly polarized light emission as described below.
２．[Eu(BIPYPO)(L-facam)3]及び[Eu(BIPYPO)(D-facam)3]の円偏光発光性
[Eu(BIPYPO)(L-facam)3]及び[Eu(BIPYPO)(D-facam)3]の円偏光発光性を求めるために、[Eu(BIPYPO)(L-facam)3]及び[Eu(BIPYPO)(D-facam)3]のCDスペクトル及びCPLスペクトルを測定した。
まず、[Eu(BIPYPO)(L-facam)3]及び[Eu(BIPYPO)(D-facam)3]のアセトニトリル溶液（1.0× 10-5M）を調製し、CDスペクトルを測定した。その結果を図７に示す。
次に、[Eu(BIPYPO)(D-facam)3]のアセトン溶液、ジメチルスルホキシド溶液、アセトニトリル溶液及びメタノール溶液（いずれも重水素溶媒、1.0M）を調製し、CPLスペクトルを測定した。その結果を図８に示す。
2. Circularly polarized luminescence of [Eu (BIPYPO) (L-facam) 3 ] and [Eu (BIPYPO) (D-facam) 3 ]
To determine the circularly polarized luminescence of [Eu (BIPYPO) (L- facam) 3] and [Eu (BIPYPO) (D- facam) 3], [Eu (BIPYPO) (L-facam) 3] and [Eu The CD spectrum and CPL spectrum of (BIPYPO) (D-facam) 3 ] were measured.
First, acetonitrile solutions (1.0 × 10 −5 M) of [Eu (BIPYPO) (L-facam) 3 ] and [Eu (BIPYPO) (D-facam) 3 ] were prepared, and CD spectra were measured. The result is shown in FIG.
Next, an acetone solution, a dimethyl sulfoxide solution, an acetonitrile solution, and a methanol solution (all of which are deuterium solvents, 1.0 M) of [Eu (BIPYPO) (D-facam) 3 ] were prepared, and CPL spectra were measured. The result is shown in FIG.
１．[Eu(BIPYPO)(D-hfbc)3]の合成
[Eu(D-hfbc)3(H2O)2]（1230mg、1.0mmol）、BIPYPO（558mgl、1.0mmol）及びメタノール100mLを200mlナスフラスコに入れ、70℃で15時間撹拌した。撹拌後、減圧下で溶媒を留去し、淡黄色の固体を得た。得られた淡黄色の固体をヘキサンに溶解させ、不溶物をろ過により取り除いた後、減圧下でろ液から溶媒を留去し、淡黄色の固体を得た。これにより、[Eu(BIPYPO)(D-hfbc) 3 ]を得た（図９）。[Eu(BIPYPO)(D-hfbc)3]の収量は1500mgであり、収率は83%であった。
1. Synthesis of [Eu (BIPYPO) (D-hfbc) 3 ]
[Eu (D-hfbc) 3 (H 2 O) 2 ] (1230 mg, 1.0 mmol), BIPYPO (558 mgl, 1.0 mmol) and 100 mL of methanol were placed in a 200 ml eggplant flask and stirred at 70 ° C. for 15 hours. After stirring, the solvent was distilled off under reduced pressure to obtain a pale yellow solid. The obtained pale yellow solid was dissolved in hexane, insoluble matters were removed by filtration, and then the solvent was distilled off from the filtrate under reduced pressure to obtain a pale yellow solid. Thus, [Eu (BIPYPO) (D-hfbc ) 3 ] was obtained (FIG. 9). The yield of [Eu (BIPYPO) (D-hfbc) 3 ] was 1500 mg, and the yield was 83%.
２．[Eu(BIPYPO)(D-hfbc)3]の発光スペクトル
[Eu(BIPYPO)(D-hfbc)3]の発光スペクトルを測定した。
[Eu(BIPYPO)(D-hfbc)3]の1mM重アセトン溶液及び1mM重アセトニトリル溶液を調製し、それぞれの溶液を体積比1：0、3：1、1：1、1：3、0：1で混合した後、これらの混合溶液について発光スペクトルを測定した。この結果を図１０に示す。
[Eu(BIPYPO)(D-hfbc)3]溶液は、いずれの混合比率においても尖鋭な発光スペクトルを示したが、アセトニトリルの比率が高くなるほど高い発光強度を示した。
2. Emission spectrum of [Eu (BIPYPO) (D-hfbc) 3 ]
The emission spectrum of [Eu (BIPYPO) (D-hfbc) 3 ] was measured.
A 1 mM heavy acetone solution and a 1 mM heavy acetonitrile solution of [Eu (BIPYPO) (D-hfbc) 3 ] are prepared, and the volume ratios of the respective solutions are 1: 0, 3: 1, 1: 1, 1: 3, 0: After mixing in 1, the emission spectra of these mixed solutions were measured. The result is shown in FIG.
The [Eu (BIPYPO) (D-hfbc) 3 ] solution showed a sharp emission spectrum at any mixing ratio, but the higher the acetonitrile ratio, the higher the emission intensity.
３．[Eu(BIPYPO)(D-hfbc)3]の円偏光発光性
[Eu(BIPYPO)(D-hfbc)3]の1mM重アセトン溶液及び1mM重アセトニトリル溶液を調製し、それぞれの溶液を体積比1：0、3：1、1：1、1：3、0：1で混合した後、これらの混合溶液についてCPLスペクトルを測定した。この結果を図１１に示す。
図１１に示すように、[Eu(BIPYPO)(D-hfbc)3]溶液は、アセトンの混合比率が低いほど（即ち、アセトニトリルの混合比率が高いほど）、高い円偏光発光性を示した。
また、上記混合溶液についてｇ値を求めた。アセトンの混合比率に対して相対発光強度 (Irel)及びｇ値をプロットしたグラフを図１２に示す。
図１２に示すように、[Eu(BIPYPO)(D-hfbc)3]は、アセトンの混合比率が高くなるほど（即ち、アセトニトリルの混合比率が低いほど）ｇ値が小さくなる傾向を示した。これは、アセトン存在下における錯体構造とアセトニトリル存在下における錯体構造が、それぞれ異なる符号のCPLを示すためと考えられる。
3. Circularly polarized luminescence of [Eu (BIPYPO) (D-hfbc) 3 ]
A 1 mM heavy acetone solution and a 1 mM heavy acetonitrile solution of [Eu (BIPYPO) (D-hfbc) 3 ] are prepared, and the volume ratios of the respective solutions are 1: 0, 3: 1, 1: 1, 1: 3, 0: After mixing in 1, CPL spectra were measured for these mixed solutions. The result is shown in FIG.
As shown in FIG. 11, the [Eu (BIPYPO) (D-hfbc) 3 ] solution exhibited higher circularly polarized light emission as the acetone mixing ratio was lower (that is, the acetonitrile mixing ratio was higher).
Moreover, g value was calculated | required about the said mixed solution. FIG. 12 is a graph plotting relative emission intensity (Irel) and g value against the mixing ratio of acetone.
As shown in FIG. 12, [Eu (BIPYPO) (D-hfbc) 3 ] showed a tendency that the g value decreased as the mixing ratio of acetone increased (that is, the mixing ratio of acetonitrile decreased). This is presumably because the complex structure in the presence of acetone and the complex structure in the presence of acetonitrile exhibit different CPLs.
これらの結果から明らかなように、上記各実施例に係るEu(III)錯体は、高い円偏光発光性だけでなく、高い発光強度を示した。また、アセトン等のケトン系溶媒とアセトニトリルの混合溶媒に上記実施例に係るEu(III)錯体を溶解して得たEu(III)錯体溶液は、混合溶媒中の混合比率に依存して異なるｇ値を示した。 As is clear from these results, the Eu (III) complexes according to the above examples exhibited not only high circularly polarized light emission but also high light emission intensity. In addition, the Eu (III) complex solution obtained by dissolving the Eu (III) complex according to the above example in a mixed solvent of a ketone solvent such as acetone and acetonitrile is different depending on the mixing ratio in the mixed solvent. The value is shown.
なお、上述した各実施例では、Ln(III)イオンとしてEu(III)を用いたが、その他、Nd、Sm、Tb、Ybを適用することも可能である。希土類イオンを適宜変更することによって、発光色が異なる円偏光発光性希土類錯体を得ることができる。 In each of the embodiments described above, Eu (III) is used as the Ln (III) ion, but Nd, Sm, Tb, and Yb can also be applied. By appropriately changing the rare earth ions, circularly polarized light-emitting rare earth complexes having different emission colors can be obtained.
また、上述した実施例では、まず８配位体の円偏光発光性希土類錯体を合成し、該錯体をケトン系溶媒に溶解することによって７配位型の円偏光発光性希土類錯体を得た。このように７配位型の円偏光発光性希土類錯体は８配位型の円偏光発光性希土類錯体を前駆体として作製することができる。また、上述した各円偏光発光性希土類錯体の合成例において、溶媒にケトン系溶媒を用いて合成を行えば８配位型を経ずに７配位型を作製することができる。７配位型の円偏光発光性希土類錯体はいずれの方法を用いても作製することが可能である。 In the above-described Examples, an 8-coordinate circularly polarized light-emitting rare earth complex was first synthesized, and the complex was dissolved in a ketone solvent to obtain a 7-coordinate circularly polarized light-emitting rare earth complex. As described above, the seven-coordinate circularly polarized light-emitting rare earth complex can be prepared using an 8-coordinated circularly polarized light-emitting rare earth complex as a precursor. In addition, in the above-described synthesis examples of each circularly polarized light-emitting rare earth complex, a 7-coordination type can be produced without going through an 8-coordination type by using a ketone solvent as a solvent. The seven-coordinate circularly polarized light-emitting rare earth complex can be produced by any method.
次に、本発明の円偏光発光性希土類錯体を利用した光学機能材料の実施例をいくつか述べる。
本発明に係る円偏光発光性希土類錯体に一方の円偏光を吸収させれば、他方の円偏光を得ることができる。即ち、円偏光板などの円偏光フィルタと同じ役割を果たすことから、本発明に係る円偏光発光性希土類錯体を円偏光フィルタに適用することが可能である。この円偏光フィルタは光多重通信など、広範な用途への適用が可能である。
また、本発明に係る円偏光発光性希土類錯体は、セキュリティインクに適用することも可能である。
本発明の円偏光発光性希土類錯体は、上記のような光学機能材料について単独で用いることができるが、７配位型と８配位型を所望の比率で含む円偏光発光性希土類錯体群を用いても良い。このような円偏光発光性希土類錯体群を用いれば、所望の円偏光発光性を有する光学機能材料を提供することができる。
Next, several examples of optical functional materials using the circularly polarized light-emitting rare earth complex of the present invention will be described.
If the circularly polarized light-emitting rare earth complex according to the present invention absorbs one circularly polarized light, the other circularly polarized light can be obtained. That is, since it plays the same role as a circularly polarizing filter such as a circularly polarizing plate, the circularly polarizing luminescent rare earth complex according to the present invention can be applied to the circularly polarizing filter. This circularly polarizing filter can be applied to a wide range of applications such as optical multiplex communication.
The circularly polarized light-emitting rare earth complex according to the present invention can also be applied to security inks.
The circularly polarized light-emitting rare earth complex of the present invention can be used alone for the optical functional materials as described above, but a circularly polarized light-emitting rare earth complex group containing a 7-coordinate type and an 8-coordinated type in a desired ratio is used. It may be used. By using such a circularly polarized light emitting rare earth complex group, an optical functional material having desired circularly polarized light emitting property can be provided.
本発明の円偏光発光性希土類錯体を上記のような光学機能材料として用いる際は、その結晶を直接用いてもよいし、透明ポリマーや透明ガラスなどの透明固体担体に含有させてもよい。また、その結晶を溶媒に溶解、分散などさせて塗料とすることもできる。 When the circularly polarized light-emitting rare earth complex of the present invention is used as an optical functional material as described above, the crystal may be used directly or may be contained in a transparent solid support such as a transparent polymer or transparent glass. Also, the crystals can be dissolved or dispersed in a solvent to form a paint.
本発明に係る円偏光発光性希土類錯体を含有させる透明ポリマーとしては、ポリメチルメタクリレート、含フッ素ポリメタクリレート、ポリアクリレート、含フッ素ポリアクリレート、ポリスチレン、ポリエチレン、ポリプロピレン、ポリブテン等のポリオレフィン、含フッ素ポリオレフィン、ポリビニルエーテル、含フッ素ポリビニルエーテル、ポリ酢酸ビニル、ポリ塩化ビニル、及びそれらの共重合体、セルロース、ポリアセタール、ポリエステル、ポリカーボネイト、エポキシ樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリウレタン、ナフィオン、石油樹脂、ロジン、ケイ素樹脂などが例示され、好ましくはポリメチルメタクリレート、含フッ素ポリメタクリレート、ポリアクリレート、含フッ素ポリアクリレート、ポリスチレン、ポリオレフィン、ポリビニルエーテル、及びそれらの共重合体、エポキシ樹脂等を使用することができる。もちろん、これらの２種以上を組み合わせたものであってもよい。
なお、本発明に係る円偏光発光性希土類錯体を含む透明ポリマーは、公知の文献（Hasegawa, et al. Chem. Lett. 1999, 35.）に従い調製することができる。
As the transparent polymer containing the circularly polarized light-emitting rare earth complex according to the present invention, polymethyl methacrylate, fluorine-containing polymethacrylate, polyacrylate, fluorine-containing polyacrylate, polystyrene, polyethylene, polypropylene, polybutene and other polyolefins, fluorine-containing polyolefin, Polyvinyl ether, fluorine-containing polyvinyl ether, polyvinyl acetate, polyvinyl chloride, and copolymers thereof, cellulose, polyacetal, polyester, polycarbonate, epoxy resin, polyamide resin, polyimide resin, polyurethane, Nafion, petroleum resin, rosin, silicon Resin, etc., preferably polymethyl methacrylate, fluorine-containing polymethacrylate, polyacrylate, fluorine-containing polyacrylate, polystyrene, polyester Olefin, polyvinyl ether, and copolymers thereof, may be used an epoxy resin or the like. Of course, it may be a combination of two or more of these.
The transparent polymer containing the circularly polarized light-emitting rare earth complex according to the present invention can be prepared according to a known document (Hasegawa, et al. Chem. Lett. 1999, 35.).
本発明の円偏光発光性希土類錯体は、その中心イオンとしての希土類イオンの種類や配位子の種類によって発光色が異なる。従って、本発明の円偏光発光性希土類錯体の希土類イオンの種類を適宜選択することにより、様々な色の発光を示す光学機能性材料を作製することができる。また、発光色を変化させるために有機色素を混合しても良い。 The circularly polarized light-emitting rare earth complex of the present invention has a different emission color depending on the type of rare earth ion as the central ion and the type of ligand. Accordingly, by appropriately selecting the type of rare earth ions of the circularly polarized light emitting rare earth complex of the present invention, optical functional materials that emit light of various colors can be produced. Further, an organic dye may be mixed in order to change the emission color.
本発明に係る円偏光発光性希土類錯体と共に溶解、分散させることのできる色素は、緑色系の色素としては、アルカリ土類シリコンオキシナイトライド系蛍光体、及びピリジン−フタルイミド縮合誘導体、ベンゾオキサジノン系、キナゾリノン系、クマリン系、キノフタロン系、ナルタル酸イミド系等の蛍光色素、テルビウム錯体等の有機蛍光体などが挙げられる。また、赤色系の色素としては、アルファサイアロン構造をもつ酸窒化物を含有する蛍光体、及びβ−ジケトネート、β−ジケトン、芳香族カルボン酸、又は、ブレンステッド酸等のアニオンを配位子とする希土類元素イオン錯体からなる赤色有機蛍光体などが挙げられる。さらに青色系の色素としては、アルカリ土類アルミネート系蛍光体、ナフタル酸イミド系、ベンゾオキサゾール系、スチリル系、クマリン系、ピラリゾン系、トリアゾール系化合物の蛍光色素、ツリウム錯体等の有機蛍光体などが挙げられる。
円偏光発光性希土類錯体は一般にカチオン性であるので、本発明に係る円偏光発光性希土類錯体と共存させる色素としては、例えばアントラセン系色素のように炭素と水素だけで構成されている色素を用いることが好ましい。
The dyes that can be dissolved and dispersed together with the circularly polarized light-emitting rare earth complex according to the present invention include, as green dyes, alkaline earth silicon oxynitride phosphors, pyridine-phthalimide condensed derivatives, and benzoxazinones. Quinazolinone-based, coumarin-based, quinophthalone-based, naltalimide-based fluorescent dyes, organic phosphors such as terbium complexes, and the like. Further, as a red dye, a phosphor containing an oxynitride having an alpha sialon structure, and an anion such as β-diketonate, β-diketone, aromatic carboxylic acid, or Bronsted acid as a ligand. Red organic phosphors composed of rare earth element ion complexes. Further, as blue dyes, alkaline earth aluminate phosphors, naphthalimide imides, benzoxazoles, styryls, coumarins, pyralizones, triazoles, fluorescent compounds, organic phosphors such as thulium complexes, etc. Is mentioned.
Since the circularly polarized light-emitting rare earth complex is generally cationic, as the dye that coexists with the circularly polarized light-emitting rare earth complex according to the present invention, for example, a dye composed only of carbon and hydrogen, such as an anthracene-based dye, is used. It is preferable.
本発明に係る円偏光発光性希土類錯体を溶解、分散させることのできる溶剤は、上記したケトン系及び非ケトン系の溶剤の他、アルコール系溶剤、エステル系溶剤或いはこれらの混合物であることが好ましい。 The solvent that can dissolve and disperse the circularly polarized light-emitting rare earth complex according to the present invention is preferably an alcohol solvent, an ester solvent, or a mixture thereof in addition to the above-mentioned ketone-based and non-ketone-based solvents. .
Claims (9)
一般式（７）
で表されることを特徴とする円偏光発光性希土類錯体。 A seven-coordinate circularly polarized light-emitting rare earth complex,
General formula (7)
In circularly polarized light emitting rare earth complex characterized by being represented.
一般式（１１）
で表されることを特徴とする円偏光発光性希土類錯体。 An eight-coordinate circularly polarized light-emitting rare earth complex,
Formula (11)
In circularly polarized light emitting rare earth complex characterized by being represented.
一般式（１２）
で表される鎖状又は環状のケトン系溶媒であることを特徴とする、請求項７に記載の円偏光発光性希土類錯体群を得る方法。 The first solvent is
Formula (12)
A method for obtaining a group of circularly polarized light-emitting rare earth complexes according to claim 7 , wherein the group is a linear or cyclic ketone solvent represented by the formula:
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