JP7335377B2 - Rare earth metal complex and light emitting device using the same - Google Patents

Description

TECHNICAL FIELD The present disclosure relates to rare earth metal complexes and light emitting devices.

Rare earth metal complexes are expected to be used as light-emitting members for fluorescent probes, laser emitters, bioimaging, sensors, security inks, and lighting. In particular, rare earth metal complexes, for example, can be excited by relatively short-wavelength blue visible light to emit long-wavelength light. It is hoped that the device can be realized. Light-emitting devices using semiconductor light-emitting elements such as light-emitting diodes (LEDs) and laser diodes (LDs) have high luminous efficiency and do not contain harmful substances such as mercury. Recently, light-emitting devices in which light-emitting diodes or laser diodes are combined with rare-earth metal complex light-emitting members have been extensively studied.

The present inventors have synthesized compositions containing new rare earth metal complexes, investigated their luminescence properties, and found that they have interesting luminescence properties, and combined them with light-emitting diodes or laser diodes for light-emitting devices. was developed and reported (see Patent Document 1 and Non-Patent Document 1).

Furthermore, various rare earth metal complex compositions have been reported that exhibit different luminous quantum efficiencies. Examples of such rare earth metal complex compositions include a rare earth metal complex having a β-diketonato ligand and a phosphine oxide ligand, a rare earth metal complex having a β-diketonato ligand and a phenanthryl ligand, Pybox ) rare earth metal complexes having a derivative ligand and a Cyclen derivative ligand (see Non-Patent Documents 2 and 3, Patent Documents 2 and 3).

Many of the above rare earth metal complexes emit light when excited by ultraviolet light (wavelength of about 280 nm to about 400 nm), but lower energy visible light (wavelength of about 400 nm to about 800 nm) such as blue light (about 450 nm) ~495 nm) and does not emit light. Therefore, normally blue light emitting diodes cannot be used as an exciting light source. Therefore, obtaining a metal complex that can be excited by blue light has also been investigated (see Non-Patent Documents 2 and 3).

In addition, X. Yang et al. synthesized a rare earth metal complex having a Schiff base and reported that its excitation wavelength has a maximum value in the ultraviolet region and that the emission is extremely low at 450 nm in the visible light region (non-patent document 4).

JP 2016-128392 A JP 2014-031348 A JP-A-2007-238650

"Chemistry-A European Journal" Vol. 17, 2011, pp. 521-528 (Chemistry-A European Journal, 2011, 17, 521-528) "Coordination Chemistry Reviews" 2015, Vol. 293-294, pp. 19-47 (Coordination Chemistry Reviews 293-294 (2015) 19-47) "Coordination Chemistry Reviews" 2014, Vol. 273-274, pp. 63-75 (Coordination Chemistry Reviews 273-274 (2014) 63-75) "Dalton Transactions" Vol. 40, 2011, pp. 9795-9801 (Dalton Transactions, 2011, 40, 9795-9801)

As the use of light-emitting devices for lighting applications is further advanced and new applications such as ink materials are being developed, new materials that can be used as wavelength conversion members such as rare earth metal complexes are in demand. For example, there is a demand for materials that have a wide excitation wavelength range and high external quantum efficiency.

Accordingly, an object of embodiments of the present invention is to provide a rare earth metal complex having a wide excitation wavelength range and high external quantum efficiency, and a method for producing the same.

［化学式（Ｉ）において、
Ａ^１は、ＯＨ基又はＳＨ基を示し、
Ａ^２は、水素、重水素、Ｃ１～Ｃ３０のアルキル基、Ｃ３～Ｃ３０のシクロアルキル基、Ｃ１～Ｃ３０のパーハロゲン化アルキル基及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基から選択され、Ｃ１～Ｃ３０のアルキル基、Ｃ３～Ｃ３０のシクロアルキル基、Ｃ１～Ｃ３０のパーハロゲン化アルキル基及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基は、下記群（Ｇ）：
芳香族基；
パーハロゲン化芳香族基；
少なくとも１種のヘテロ原子を環中に含むヘテロ芳香族基；
直鎖又は分枝を有するＣ１～Ｃ３０のアルキル基；
直鎖又は分枝を有するＣ１～Ｃ３０のパーハロゲン化アルキル基；
直鎖又は分枝を有するＣ３～Ｃ３０のアルケニル基；
直鎖又は分枝を有するＣ３～Ｃ３０のパーハロゲン化アルケニル基；
Ｃ３～Ｃ３０のシクロアルキル基；
Ｃ３～Ｃ３０のパーハロゲン化シクロアルキル基；
Ｃ３～Ｃ３０のシクロアルケニル基；
Ｃ３～Ｃ３０のパーハロゲン化シクロアルケニル基；及び
Ｃ３～Ｃ３０のアルキニル基、並びに
ハロゲノ基から選択される一又は複数の置換基を有することができ、
Ａ^３は、Ｃ２～Ｃ３０のアルキレン基から選択され、そのアルキレン基は、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができ、
Ａ^１とアゾメチン基が共に結合するベンゼン環について、Ａ^１とアゾメチン基が結合していない、ベンゼン環の隣接する２つの炭素原子は、－Ｃ_４Ｈ_４－で接続されてナフタレン環を形成することができ、
そのベンゼン環と形成され得るナフタレン環は、両方共、更に、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができる］
で示される、二組の水酸基又はチオール基とアゾメチン基を有する配位子；及び

化学式（ＩＩ）：

［化学式（ＩＩ）において、
Ａ^１及びＡ^２は、化学式（Ｉ）のものと同じであり、
Ａ^４は、Ｃ１～Ｃ３０のアルキル基から選択され、そのアルキル基は、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができ、
Ａ^１とアゾメチン基が共に結合するベンゼン環について、化学式（Ｉ）のベンゼン環と同様にナフタレン環を形成してよく、
そのベンゼン環と形成され得るナフタレン環は、両方共、更に、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができる］
で示される、一組の水酸基又はチオール基とアゾメチン基を有する配位子からなる群から選択される、水酸基又はチオール基とアゾメチン基を共に有する配位子、並びに

化学式（ＩＩＩ）

［化学式（ＩＩＩ）において、
Ｘは、両方共同一であっても各々が異なってもよい、上記群（Ｇ）から選択される置換基を示し、
Ｚは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、シアノ基、メチル基、エチル基、フェニル基、水素原子又は重水素原子を示す］
で示されるβ－ジケトナト配位子
が、共に配位し、

過塩素酸イオン、硝酸イオン、カルボン酸イオン、及びハロゲン化物イオンから選択される少なくとも１種の陰イオンが更に配位してよい、
希土類金属を含む、希土類金属錯体を提供する。 In one embodiment according to the invention,
Chemical formula (I):

[In the chemical formula (I),
A ¹ represents an OH group or an SH group,
A ² is selected from hydrogen, deuterium, C1-C30 alkyl groups, C3-C30 cycloalkyl groups, C1-C30 perhalogenated alkyl groups and C3-C30 perhalogenated cycloalkyl groups; The C30 alkyl group, the C3-C30 cycloalkyl group, the C1-C30 perhalogenated alkyl group and the C3-C30 perhalogenated cycloalkyl group are selected from the following group (G):
aromatic group;
perhalogenated aromatic groups;
heteroaromatic groups containing at least one heteroatom in the ring;
C1-C30 alkyl group having a straight or branched chain;
a C1-C30 perhalogenated alkyl group having a straight or branched chain;
straight or branched C3-C30 alkenyl group;
straight or branched C3-C30 perhalogenated alkenyl group;
C3-C30 cycloalkyl group;
a C3-C30 perhalogenated cycloalkyl group;
C3-C30 cycloalkenyl group;
C3-C30 perhalogenated cycloalkenyl groups; and C3-C30 alkynyl groups, and halogeno groups.
A ³ is selected from C2-C30 alkylene groups, which alkylene groups may have one or more substituents selected from the above group (G) and halogeno groups,
For the benzene ring to which A ¹ and the azomethine group are bonded together, two adjacent carbon atoms of the benzene ring to which A ¹ and the azomethine group are not bonded are connected by —C ₄ H ₄ — to form a naphthalene ring. It is possible,
Both the benzene ring and the naphthalene ring that can be formed can further have one or more substituents selected from the above group (G) and a halogeno group]
a ligand having two sets of hydroxyl or thiol groups and an azomethine group; and

Chemical formula (II):

[In the chemical formula (II),
A ¹ and A ² are the same as those of formula (I);
A ⁴ is selected from C1 to C30 alkyl groups, which alkyl groups may have one or more substituents selected from the above group (G) and halogeno groups;
Regarding the benzene ring to which ^A1 and the azomethine group are bonded together, a naphthalene ring may be formed in the same manner as the benzene ring of the chemical formula (I),
Both the benzene ring and the naphthalene ring that can be formed can further have one or more substituents selected from the above group (G) and a halogeno group]
A ligand having both a hydroxyl group or a thiol group and an azomethine group, selected from the group consisting of ligands having a set of hydroxyl or thiol groups and an azomethine group, and

chemical formula (III)

[In the chemical formula (III),
X represents a substituent selected from the above group (G), both of which may be the same or each may be different;
Z represents a fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, methyl group, ethyl group, phenyl group, hydrogen atom or deuterium atom]
β-diketonato ligands represented by are coordinated together,

at least one anion selected from perchlorate ions, nitrate ions, carboxylate ions, and halide ions may be further coordinated;
A rare earth metal complex comprising a rare earth metal is provided.

The present embodiment can provide a rare earth metal complex having a wide excitation wavelength region and high external quantum efficiency, and a method for producing the same.

FIG. 1 shows chemical formulas of ligands of embodiments of the present invention. FIG. 2 shows the chemical structures involved in rare earth metal complexes according to embodiments of the present invention. 3 shows an ORTEP diagram of the Eu(H ₂ salen) ₂ (hfa ⁻ ) ₂ (CH ₃ COO ⁻ ) complex of Example 1. FIG. 4 shows the ORTEP diagram of the Eu ₂ (H ₂ 1,4-salbn) ₂ (hfa ⁻ ) ₄ (CH ₃ COO ⁻ ) ₂ complex of Example 2. FIG. 5 shows the ORTEP diagram of the [Eu(H ₂ 1,6-salhxn)(hfa ⁻ ) ₂ (CH ₃ COO ⁻ )]n complex of Example 3. FIG. 6 shows the Eu ₄ (H ₂ 1,4-salbn) ₄ (btfa ⁻ ) ₁₂ complex ORTEP diagram of Example 4. FIG. 7 shows excitation spectra of the complexes of Examples 1 to 4 and Comparative Example 1. FIG. 8a shows the emission spectra of the complexes of Examples 1-4 and Comparative Example 1. FIG. FIG. 8b shows a magnified portion of the emission spectrum of FIG. 8a. 9 shows reflectance spectra of the complexes of Examples 1-4 and Comparative Example 1. FIG. FIG. 10 shows the emission spectrum of a light-emitting device manufactured by mounting a transparent solid carrier obtained by dispersing the complex of Example 2 in a silicone resin on a blue light-emitting diode.

Hereinafter, with reference to the accompanying drawings, a rare earth metal complex containing a rare earth metal in which a ligand having a hydroxyl group or a thiol group and an azomethine group and a β-diketonato ligand of the embodiment of the present invention are coordinated together, and A transparent fixing carrier for an optical functional material including it will be described in detail.

［化学式（Ｉ）において、
Ａ^１は、ＯＨ基又はＳＨ基を示し、
Ａ^２は、水素、重水素、Ｃ１～Ｃ３０のアルキル基（－Ｃ_ｎＨ_２ｎ＋１：ここでｎ＝１～３０、好ましくはｎ＝１～１８、より好ましくはｎ＝１～６、特に好ましくはｎ＝１～３）、Ｃ３～Ｃ３０のシクロアルキル基（－Ｃ_ｎＨ_２ｎ－１：ここでｎ＝３～３０、好ましくはｎ＝３～１８、より好ましくはｎ＝３～６、特に好ましくはｎ＝３）、Ｃ１～Ｃ３０のパーハロゲン化アルキル基（－Ｃ_ｎＦ_２ｎ＋１及び－Ｃ_ｎＣｌ_２ｎ＋１等、好ましくは－Ｃ_ｎＦ_２ｎ＋１：ここでｎ＝１～３０、好ましくはｎ＝１～１８、より好ましくはｎ＝１～６、特に好ましくはｎ＝１～３）及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基（－Ｃ_ｎＦ_２ｎ－１及び－Ｃ_ｎＣｌ_２ｎ－１等、好ましくは－Ｃ_ｎＦ_２ｎ－１：ここでｎ＝３～３０、好ましくはｎ＝３～１８、より好ましくはｎ＝３～６、特に好ましくはｎ＝３）から選択され、Ｃ１～Ｃ３０のアルキル基、Ｃ３～Ｃ３０のシクロアルキル基、Ｃ１～Ｃ３０のパーハロゲン化アルキル基及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基は、下記群（Ｇ１）：
フェニル基、ナフチル基及びビフェニル基等の芳香族基；
パーフルオロフェニル基、パーフルオロナフチル基、パーフルオロビフェニル基、パークロロフェニル基、パークロロナフチル基、及びパークロロビフェニル基等のパーハロゲン化芳香族基；
Ｎ、Ｏ、及びＳ等から選択される少なくとも１種のヘテロ原子を環中に含むヘテロ芳香族基；
直鎖又は分枝を有するＣ１～Ｃ３０のアルキル基（Ｃ_ｎＨ_２ｎ＋１：ｎ＝１～３０）；
パーフルオロアルキル基（Ｃ_ｎＦ_２ｎ＋１：ｎ＝１～３０）及びパークロロアルキル基（Ｃ_ｎＣｌ_２ｎ＋１：ｎ＝１～３０）等の、直鎖又は分枝を有するＣ１～Ｃ３０のパーハロゲン化アルキル基；
ブテニル基等の直鎖又は分枝を有するＣ３～Ｃ３０のアルケニル基；
パーフルオロビニル基、パーフルオロアリル基及びパーフルオロブテニル基等のパーフルオロアルケニル基及びパークロロアルケニル基等の、直鎖又は分枝を有するＣ３～Ｃ３０のパーハロゲン化アルケニル基；
Ｃ３～Ｃ３０のシクロアルキル基（Ｃ_ｎＨ_２ｎ－１：ｎ＝３～３０）；
パーフルオロシクロアルキル基（Ｃ_ｎＦ_２ｎ－１：ｎ＝３～３０）及びパークロロシクロアルキル基（Ｃ_ｎＣｌ_２ｎ－１：ｎ＝３～３０）等のＣ３～Ｃ３０のパーハロゲン化シクロアルキル基；
シクロペンテニル基及びシクロヘキセニル基等のＣ３～Ｃ３０のシクロアルケニル基；
パーフルオロシクロアルケニル基及びパークロロシクロアルケニル基等のＣ３～Ｃ３０のパーハロゲン化シクロアルケニル基；及び
Ｃ３～Ｃ３０のアルキニル基、並びに
ハロゲノ基（例えば、Ｆ、Ｃｌ等、好ましくはＦ）から選択される一又は複数の置換基を有することができ、
Ａ^３は、Ｃ２～Ｃ３０のアルキレン基（－Ｃ_ｎＨ_２ｎ－：ここでｎ＝２～３０、好ましくは、ｎ＝４～１２）から選択され、そのアルキレン基は、上記群（Ｇ１）並びにハロゲノ基（例えば、Ｆ、Ｃｌ等、好ましくはＦ）から選択される一又は複数の置換基を有することができ、
Ａ^１とアゾメチン基が共に結合するベンゼン環について、Ａ^１とアゾメチン基が結合していない、ベンゼン環の隣接する２つの炭素原子は、－Ｃ_４Ｈ_４－で接続されてナフタレン環を形成することができ、
そのベンゼン環と形成され得るナフタレン環は、両方共、更に、上記群（Ｇ１）並びにハロゲノ基（例えば、Ｆ、Ｃｌ等、好ましくはＦ）から選択される一又は複数の置換基を有することができる］
で示される、二組の水酸基又はチオール基とアゾメチン基を有する配位子；及び

化学式（ＩＩ）：

［化学式（ＩＩ）において、
Ａ^１及びＡ^２は、化学式（Ｉ）のものと同じであり、
Ａ^４は、Ｃ１～３０のアルキル基（－Ｃ_ｎＨ_２ｎ＋１：ここでｎ＝１～３０、好ましくはｎ＝１～１８）から選択され、そのアルキル基は、上記群（Ｇ１）並びにハロゲノ基（例えば、Ｆ、Ｃｌ等、好ましくはＦ）から選択される一又は複数の置換基を有することができ、
Ａ^１とアゾメチン基が共に結合するベンゼン環について、化学式（Ｉ）のベンゼン環と同様にナフタレン環を形成してよく、
そのベンゼン環と形成され得るナフタレン環は、両方共、更に、上記群（Ｇ１）並びにハロゲノ基（例えば、Ｆ、Ｃｌ等、好ましくはＦ）から選択される一又は複数の置換基を有することができる］
で示される、一組の水酸基又はチオール基とアゾメチン基を有する配位子からなる群から選択される、水酸基又はチオール基とアゾメチン基を共に有する配位子、並びに

化学式（ＩＩＩ）

［化学式（ＩＩＩ）において、
Ｘは、両方共同一であっても各々が異なってもよい、上記群（Ｇ１）から選択される置換基を示し、
Ｚは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、シアノ基、メチル基、エチル基、フェニル基、水素原子又は重水素原子を示す］
で示されるβ－ジケトナト配位子
が、共に配位し、

過塩素酸イオン、硝酸イオン、カルボン酸イオン、及びハロゲン化物イオンから選択される少なくとも１種の陰イオンが更に配位してよい、
希土類金属を含む。 The rare earth metal complex of the embodiment of the present invention is
Chemical formula (I):

[In the chemical formula (I),
A ¹ represents an OH group or an SH group,
A ² is hydrogen, deuterium, or a C1-C30 alkyl group (—C _n H _2n+1 : where n=1-30, preferably n=1-18, more preferably n=1-6, particularly preferably n=1-3), a C3-C30 cycloalkyl group (—C _n H _2n-1 : where n=3-30, preferably n=3-18, more preferably n=3-6, particularly preferably C1-C30 perhalogenated alkyl groups (-C _n F _2n+1 and -C _n Cl _2n+1 , etc., preferably -C _n F _2n+1 : where n=1-30, preferably n=1 to 18, more preferably n=1-6, particularly preferably n=1-3) and C3-C30 perhalogenated cycloalkyl groups (—C _n F _2n-1 and —C _n Cl _2n-1 , etc., preferably -C _n F _2n-1 : wherein n=3 to 30, preferably n=3 to 18, more preferably n=3 to 6, particularly preferably n=3); Alkyl groups, C3-C30 cycloalkyl groups, C1-C30 perhalogenated alkyl groups and C3-C30 perhalogenated cycloalkyl groups are selected from the following group (G1):
aromatic groups such as phenyl, naphthyl and biphenyl groups;
Perhalogenated aromatic groups such as perfluorophenyl, perfluoronaphthyl, perfluorobiphenyl, perchlorophenyl, perchloronaphthyl, and perchlorobiphenyl groups;
a heteroaromatic group containing at least one heteroatom selected from N, O, S, etc. in the ring;
linear or branched C1-C30 alkyl group (C _n H _2n+1 : n=1-30);
C1-C30 perhalogenation with linear or branched chain such as perfluoroalkyl group (C _n F _{2n +1} : n=1-30) and perchloroalkyl group (C _n Cl 2n+1 : n=1-30) alkyl group;
straight or branched C3-C30 alkenyl groups such as butenyl groups;
linear or branched C3-C30 perhalogenated alkenyl groups such as perfluoroalkenyl groups and perchloroalkenyl groups such as perfluorovinyl groups, perfluoroallyl groups and perfluorobutenyl groups;
a C3-C30 cycloalkyl group (C _n H _2n-1 : n=3-30);
C3-C30 perhalogenated cycloalkyls such as perfluorocycloalkyl groups (C _n F _2n-1 : n=3-30) and perchlorocycloalkyl groups (C _n Cl _2n-1 : n=3-30) group;
C3-C30 cycloalkenyl groups such as a cyclopentenyl group and a cyclohexenyl group;
C3-C30 perhalogenated cycloalkenyl groups such as perfluorocycloalkenyl groups and perchlorocycloalkenyl groups; and C3-C30 alkynyl groups, and halogeno groups (eg, F, Cl, etc., preferably F) can have one or more substituents that
A ³ is selected from a C2 to C30 alkylene group (-C _n H _2n -, where n = 2 to 30, preferably n = 4 to 12), and the alkylene group is selected from the above group (G1) as well as can have one or more substituents selected from halogeno groups (e.g., F, Cl, etc., preferably F);
For the benzene ring to which A ¹ and the azomethine group are bonded together, two adjacent carbon atoms of the benzene ring to which A ¹ and the azomethine group are not bonded are connected by —C ₄ H ₄ — to form a naphthalene ring. It is possible,
Both the benzene ring and the naphthalene ring that can be formed further have one or more substituents selected from the above group (G1) and halogeno groups (e.g., F, Cl, etc., preferably F). can]
a ligand having two sets of hydroxyl or thiol groups and an azomethine group; and

Chemical formula (II):

[In the chemical formula (II),
A ¹ and A ² are the same as those of formula (I);
A ⁴ is selected from a C1-30 alkyl group (-C _n H _2n+1 : where n=1-30, preferably n=1-18), the alkyl group being selected from the above group (G1) as well as a halogeno group can have one or more substituents selected from (e.g. F, Cl, etc., preferably F),
The benzene ring to which ^A1 and the azomethine group are bonded together may form a naphthalene ring in the same manner as the benzene ring of the chemical formula (I),
Both the benzene ring and the naphthalene ring that can be formed further have one or more substituents selected from the above group (G1) and halogeno groups (e.g., F, Cl, etc., preferably F). can]
a ligand having both a hydroxyl group or a thiol group and an azomethine group, selected from the group consisting of ligands having a hydroxyl group or a thiol group and an azomethine group, and

chemical formula (III)

[In the chemical formula (III),
X represents a substituent selected from the above group (G1), both of which may be the same or each may be different;
Z represents a fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, methyl group, ethyl group, phenyl group, hydrogen atom or deuterium atom]
β-diketonato ligands represented by are coordinated together,

at least one anion selected from perchlorate ions, nitrate ions, carboxylate ions, and halide ions may be further coordinated;
Contains rare earth metals.

A dashed line is drawn for one A ¹ of the ligand of formula (I), A ¹ of the ligand of formula (II) and two oxygens of the ligand of formula (III). Each dotted line indicates the formation of one coordinate bond with the rare earth metal. Thus, the β-diketonato ligand is shown to form a total of two coordinate bonds. The other ^A1 in chemical formula (I) has no dotted line. This indicates that a coordinate bond may or may not be formed.

［化学式（ＩＶ）において、
Ｌｎは、希土類金属原子を示し、ｎ１は、２又は３を示し、

β－ジケトナト配位子について、Ｘは、両方共同一であっても各々が異なってもよい、下記群（Ｇ１）：
フェニル基、ナフチル基及びビフェニル基等の芳香族基；
パーフルオロフェニル基、パーフルオロナフチル基、パーフルオロビフェニル基、パークロロフェニル基、パークロロナフチル基、及びパークロロビフェニル基等のパーハロゲン化芳香族基；
Ｎ、Ｏ、及びＳ等から選択される少なくとも１種のヘテロ原子を環中に含むヘテロ芳香族基；
直鎖又は分枝を有するＣ１～Ｃ３０のアルキル基（Ｃ_ｎＨ_２ｎ＋１：ｎ＝１～３０）；
パーフルオロアルキル基（Ｃ_ｎＦ_２ｎ＋１：ｎ＝１～３０）及びパークロロアルキル基（Ｃ_ｎＣｌ_２ｎ＋１：ｎ＝１～３０）等の直鎖又は分枝を有するＣ１～Ｃ３０のパーハロゲン化アルキル基；
ブテニル基等の直鎖又は分枝を有するＣ３～Ｃ３０のアルケニル基；
パーフルオロビニル基、パーフルオロアリル基及びパーフルオロブテニル基等のパーフルオロアルケニル基及びパークロロアルケニル基等の直鎖又は分枝を有するＣ３～Ｃ３０のパーハロゲン化アルケニル基；
Ｃ３～Ｃ３０のシクロアルキル基（Ｃ_ｎＨ_２ｎ－１：ｎ＝３～３０）；
パーフルオロシクロアルキル基（Ｃ_ｎＦ_２ｎ－１：ｎ＝３～３０）及びパークロロシクロアルキル基（Ｃ_ｎＣｌ_２ｎ－１：ｎ＝３～３０）等のＣ３～Ｃ３０のパーハロゲン化シクロアルキル基；
シクロペンテニル基及びシクロヘキセニル基等のＣ３～Ｃ３０のシクロアルケニル基；
パーフルオロシクロアルケニル基及びパークロロシクロアルケニル基等のＣ３～Ｃ３０のパーハロゲン化シクロアルケニル基；及び
Ｃ３～Ｃ３０のアルキニル基、
から選択される置換基を示し
Ｚは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、シアノ基、メチル基、エチル基、フェニル基、水素原子又は重水素原子を示し、ｎ２は、１～３の整数を示し、

Ｙは、過塩素酸イオン、硝酸イオン、カルボン酸イオン、及びハロゲン化物イオンから選択される少なくとも１種でありえ、ｎ３は、０～２の整数を示し、

二組の水酸基又はチオール基とアゾメチン基を有する配位子について、
Ａ^１は、ＯＨ基又はＳＨ基を示し、
Ａ^２は、水素、重水素、Ｃ１～Ｃ３０のアルキル基（－Ｃ_ｎＨ_２ｎ＋１：ここでｎ＝１～３０、好ましくはｎ＝１～１８、より好ましくはｎ＝１～６、特に好ましくはｎ＝１～３）、Ｃ３～Ｃ３０のシクロアルキル基（－Ｃ_ｎＨ_２ｎ－１：ここでｎ＝３～３０、好ましくはｎ＝３～１８、より好ましくはｎ＝３～６、特に好ましくはｎ＝３）、Ｃ１～Ｃ３０のパーハロゲン化アルキル基（－Ｃ_ｎＦ_２ｎ＋１及び－Ｃ_ｎＣｌ_２ｎ＋１等、好ましくは－Ｃ_ｎＦ_２ｎ＋１：ここでｎ＝１～３０、好ましくはｎ＝１～１８、より好ましくはｎ＝１～６、特に好ましくはｎ＝１～３）及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基（－Ｃ_ｎＦ_２ｎ－１及び－Ｃ_ｎＣｌ_２ｎ－１等、好ましくは－Ｃ_ｎＦ_２ｎ－１：ここでｎ＝３～３０、好ましくはｎ＝３～１８、より好ましくはｎ＝３～６、特に好ましくはｎ＝３）から選択され、Ｃ１～Ｃ３０のアルキル基、Ｃ３～Ｃ３０のシクロアルキル基、Ｃ１～Ｃ３０のパーハロゲン化アルキル基及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基は、上記群（Ｇ１）並びにハロゲノ基（例えば、Ｆ、Ｃｌ等、好ましくはＦ）から選択される一又は複数の置換基を有することができ、
Ａ^３は、Ｃ２～Ｃ３０のアルキレン基（－Ｃ_ｎＨ_２ｎ－：ここでｎ＝２～３０、好ましくは、ｎ＝４～１２）から選択され、そのアルキレン基は、上記群（Ｇ１）並びにハロゲノ基（例えば、Ｆ、Ｃｌ等、好ましくはＦ）から選択される一又は複数の置換基を有することができ、
Ａ^１とアゾメチン基が共に結合するベンゼン環について、Ａ^１とアゾメチン基が結合していない、ベンゼン環の隣接する２つの炭素原子は、－Ｃ_４Ｈ_４－で接続されてナフタレン環を形成することができ、
そのベンゼン環と形成され得るナフタレン環は、両方共、更に、上記群（Ｇ１）並びにハロゲノ基（例えば、Ｆ、Ｃｌ等、好ましくはＦ）から選択される一又は複数の置換基を有することができ、
ｎ４は、１～３の整数を示す］、

化学式（Ｖ）：

［化学式（Ｖ）において、
ｎ５は、２以上の整数を示すほかは、化学式（ＩＶ）のものと同様である］、

化学式（ＶＩ）：

［化学式（ＶＩ）において、
ｎ６は、１以上の整数を示すほかは、化学式（ＩＶ）のものと同様である］、

化学式（ＶＩＩ）：

［化学式（ＶＩＩ）において、
一組の水酸基又はチオール基とアゾメチン基を有する配位子について、
Ａ^１は、ＯＨ基又はＳＨ基を示し、
Ａ^２は、水素、重水素、Ｃ１～Ｃ３０のアルキル基（－Ｃ_ｎＨ_２ｎ＋１：ここでｎ＝１～３０、好ましくはｎ＝１～１８、より好ましくはｎ＝１～６、特に好ましくはｎ＝１～３）、Ｃ３～Ｃ３０のシクロアルキル基（－Ｃ_ｎＨ_２ｎ－１：ここでｎ＝３～３０、好ましくはｎ＝３～１８、より好ましくはｎ＝３～６、特に好ましくはｎ＝３）、Ｃ１～Ｃ３０のパーハロゲン化アルキル基（－Ｃ_ｎＦ_２ｎ＋１及び－Ｃ_ｎＣｌ_２ｎ＋１等、好ましくは－Ｃ_ｎＦ_２ｎ＋１：ここでｎ＝１～３０、好ましくはｎ＝１～１８、より好ましくはｎ＝１～６、特に好ましくはｎ＝１～３）及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基（－Ｃ_ｎＦ_２ｎ－１及び－Ｃ_ｎＣｌ_２ｎ－１等、好ましくは－Ｃ_ｎＦ_２ｎ－１：ここでｎ＝３～３０、好ましくはｎ＝３～１８、より好ましくはｎ＝３～６、特に好ましくはｎ＝３）から選択され、Ｃ１～Ｃ３０のアルキル基、Ｃ３～Ｃ３０のシクロアルキル基、Ｃ１～Ｃ３０のパーハロゲン化アルキル基及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基は、上記群（Ｇ１）並びにハロゲノ基（例えば、Ｆ、Ｃｌ等、好ましくはＦ）を含む群から選択される一又は複数の置換基を有することができ、
Ａ^４は、Ｃ１～３０のアルキル基（－Ｃ_ｎＨ_２ｎ＋１：ここでｎ＝１～３０、好ましくはｎ＝１～１８）から選択され、そのアルキル基は、上記群（Ｇ１）並びにハロゲノ基（例えば、Ｆ、Ｃｌ等、好ましくはＦ）を含む群から選択される一又は複数の置換基を有することができ、
Ａ^１とアゾメチン基が共に結合するベンゼン環について、化学式（ＩＶ）と同様にナフタレン環を形成してよく、
そのベンゼン環と形成され得るナフタレン環は、両方共、更に、上記群（Ｇ１）並びにハロゲノ基（例えば、Ｆ、Ｃｌ等、好ましくはＦ）を含む群から選択される一又は複数の置換基を有することができ、
ｎ４は、１～３の整数を示す
ほかは、化学式（ＩＶ）のものと同様である］。 Furthermore, the rare earth metal complexes of embodiments of the present invention are
It preferably contains at least one chemical structure selected from chemical structures represented by the following chemical formulas (IV), (V), (VI), and (VII).
Chemical formula (IV):

[In the chemical formula (IV),
Ln represents a rare earth metal atom, n1 represents 2 or 3,

For β-diketonato ligands, X may both be the same or each be different, the following group (G1):
aromatic groups such as phenyl, naphthyl and biphenyl groups;
Perhalogenated aromatic groups such as perfluorophenyl, perfluoronaphthyl, perfluorobiphenyl, perchlorophenyl, perchloronaphthyl, and perchlorobiphenyl groups;
a heteroaromatic group containing at least one heteroatom selected from N, O, S, etc. in the ring;
linear or branched C1-C30 alkyl group (C _n H _2n+1 : n=1-30);
Linear or branched C1-C30 perhalogenated alkyl such as perfluoroalkyl group (C _n F _2n+1 : n=1 to 30) and perchloroalkyl group (C _n Cl _2n+ 1 : n=1 to 30) group;
straight or branched C3-C30 alkenyl groups such as butenyl groups;
straight or branched C3-C30 perhalogenated alkenyl groups such as perfluoroalkenyl groups and perchloroalkenyl groups such as perfluorovinyl groups, perfluoroallyl groups and perfluorobutenyl groups;
a C3-C30 cycloalkyl group (C _n H _2n-1 : n=3-30);
C3-C30 perhalogenated cycloalkyls such as perfluorocycloalkyl groups (C _n F _2n-1 : n=3-30) and perchlorocycloalkyl groups (C _n Cl _2n-1 : n=3-30) group;
C3-C30 cycloalkenyl groups such as a cyclopentenyl group and a cyclohexenyl group;
C3-C30 perhalogenated cycloalkenyl groups such as perfluorocycloalkenyl groups and perchlorocycloalkenyl groups; and C3-C30 alkynyl groups,
Z represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a methyl group, an ethyl group, a phenyl group, a hydrogen atom or a deuterium atom, and n2 represents 1 to 3 indicates an integer of

Y can be at least one selected from perchlorate ions, nitrate ions, carboxylate ions, and halide ions, n3 is an integer of 0 to 2,

For ligands having two pairs of hydroxyl or thiol groups and an azomethine group,
A ¹ represents an OH group or an SH group,
A ² is hydrogen, deuterium, or a C1-C30 alkyl group (—C _n H _2n+1 : where n=1-30, preferably n=1-18, more preferably n=1-6, particularly preferably n=1-3), a C3-C30 cycloalkyl group (—C _n H _2n-1 : where n=3-30, preferably n=3-18, more preferably n=3-6, particularly preferably C1-C30 perhalogenated alkyl groups (-C _n F _2n+1 and -C _n Cl _2n+1 , etc., preferably -C _n F _2n+1 : where n=1-30, preferably n=1 to 18, more preferably n=1-6, particularly preferably n=1-3) and C3-C30 perhalogenated cycloalkyl groups (—C _n F _2n-1 and —C _n Cl _2n-1 , etc., preferably -C _n F _2n-1 : wherein n=3 to 30, preferably n=3 to 18, more preferably n=3 to 6, particularly preferably n=3); Alkyl groups, C3-C30 cycloalkyl groups, C1-C30 perhalogenated alkyl groups and C3-C30 perhalogenated cycloalkyl groups are selected from the above group (G1) and halogeno groups (e.g., F, Cl, etc., preferably can have one or more substituents selected from F),
A ³ is selected from a C2 to C30 alkylene group (-C _n H _2n -, where n = 2 to 30, preferably n = 4 to 12), and the alkylene group is selected from the above group (G1) as well as can have one or more substituents selected from halogeno groups (e.g., F, Cl, etc., preferably F);
For the benzene ring to which A ¹ and the azomethine group are bonded together, two adjacent carbon atoms of the benzene ring to which A ¹ and the azomethine group are not bonded are connected by —C ₄ H ₄ — to form a naphthalene ring. It is possible,
Both the benzene ring and the naphthalene ring that can be formed further have one or more substituents selected from the above group (G1) and halogeno groups (e.g., F, Cl, etc., preferably F). can
n4 represents an integer of 1 to 3],

Chemical formula (V):

[In the chemical formula (V),
n5 is the same as that of chemical formula (IV) except that it represents an integer of 2 or more],

Chemical formula (VI):

[In the chemical formula (VI),
n6 is the same as that of chemical formula (IV) except that it represents an integer of 1 or more],

Chemical formula (VII):

[In the chemical formula (VII),
For a ligand having a pair of hydroxyl or thiol groups and an azomethine group,
A ¹ represents an OH group or an SH group,
A ² is hydrogen, deuterium, or a C1-C30 alkyl group (—C _n H _2n+1 : where n=1-30, preferably n=1-18, more preferably n=1-6, particularly preferably n=1-3), a C3-C30 cycloalkyl group (—C _n H _2n-1 : where n=3-30, preferably n=3-18, more preferably n=3-6, particularly preferably C1-C30 perhalogenated alkyl groups (-C _n F _2n+1 and -C _n Cl _2n+1 , etc., preferably -C _n F _2n+1 : where n=1-30, preferably n=1 to 18, more preferably n=1-6, particularly preferably n=1-3) and C3-C30 perhalogenated cycloalkyl groups (—C _n F _2n-1 and —C _n Cl _2n-1 , etc., preferably -C _n F _2n-1 : wherein n=3 to 30, preferably n=3 to 18, more preferably n=3 to 6, particularly preferably n=3); Alkyl groups, C3-C30 cycloalkyl groups, C1-C30 perhalogenated alkyl groups and C3-C30 perhalogenated cycloalkyl groups are selected from the above group (G1) and halogeno groups (e.g., F, Cl, etc., preferably can have one or more substituents selected from the group comprising F),
A ⁴ is selected from a C1-30 alkyl group (-C _n H _2n+1 : where n=1-30, preferably n=1-18), the alkyl group being selected from the above group (G1) as well as a halogeno group can have one or more substituents selected from the group comprising (e.g., F, Cl, etc., preferably F),
The benzene ring to which ^A1 and the azomethine group are bonded together may form a naphthalene ring in the same manner as in chemical formula (IV),
Both the benzene ring and the naphthalene ring that can be formed further have one or more substituents selected from the group including the above group (G1) and a halogeno group (e.g., F, Cl, etc., preferably F). can have
n4 is the same as that of chemical formula (IV), except that n4 represents an integer of 1 to 3].

Furthermore, the dotted line between A1 ^and Ln and the dotted line between O and Ln in chemical formulas (IV) to (VII) each represent one coordinate bond. Therefore, the β-diketonato ligand forms two coordinate bonds with the rare earth metal.
On the other hand, since the number of coordination bonds that Y can form with a rare earth metal can vary from 1 to 3, the line between Y and Ln is not just a dotted line but a wide dotted line (hashed line ).

Having both a hydroxyl group or a thiol group (A ¹ ) of chemical formulas (I) to (II) and an azomethine group (or Schiff base: -CA ² =N-) included in chemical structures of chemical formulas (IV) to (VII) The ligand will be further explained.
The ligands of formula (I) have two pairs of hydroxyl or thiol groups and an azomethine group, and the ligands of formula (II) have one pair of hydroxyl or thiol groups and an azomethine group.
The ligands of the chemical formulas (I) to (II) coordinate to the rare earth metal atom with a hydroxyl group (OH) or a thiol group (SH) indicated by ^A1 .

Both the hydroxyl group or thiol group (A ¹ ) and the azomethine group are bonded to a benzene ring, and the benzene ring may further form a naphthalene ring.
The positions of the hydroxyl group or thiol group (A ¹ ) and the azomethine group are not particularly limited as long as the desired complex can be obtained, and may be o-substituted, m-substituted, p-substituted, or the like. , o-substitution is more preferable from the viewpoint of emission properties.
A carbon atom of the azomethine group can have a substituent ^A2 . A ² is hydrogen, deuterium, or a C1-C30 alkyl group (—C _n H _2n+1 : where n=1-30, preferably n=1-18, more preferably n=1-6, particularly preferably n=1-3), a C3-C30 cycloalkyl group (—C _n H _2n-1 : where n=3-30, preferably n=3-18, more preferably n=3-6, particularly preferably C1-C30 perhalogenated alkyl groups (-C _n F _2n+1 and -C _n Cl _2n+1 , etc., preferably -C _n F _2n+1 : where n=1-30, preferably n=1 to 18, more preferably n=1-6, particularly preferably n=1-3) and C3-C30 perhalogenated cycloalkyl groups (—C _n F _2n-1 and —C _n Cl _2n-1 , etc., preferably -C _n F _2n-1 : wherein n=3 to 30, preferably n=3 to 18, more preferably n=3 to 6, particularly preferably n=3).

The C1-C30 alkyl group, C3-C30 cycloalkyl group, C1-C30 perhalogenated alkyl group and C3-C30 perhalogenated cycloalkyl group of A ² are selected from the following group (G1):
aromatic groups such as phenyl, naphthyl and biphenyl groups;
Perhalogenated aromatic groups such as perfluorophenyl, perfluoronaphthyl, perfluorobiphenyl, perchlorophenyl, perchloronaphthyl, and perchlorobiphenyl groups;
a heteroaromatic group containing at least one heteroatom selected from N, O, S, etc. in the ring;
linear or branched C1-C30 alkyl group (C _n H _2n+1 : n=1-30);
Linear or branched C1-C30 perhalogenated alkyl such as perfluoroalkyl group (C _n F _2n+1 : n=1 to 30) and perchloroalkyl group (C _n Cl _2n+ 1 : n=1 to 30) group;
straight or branched C3-C30 alkenyl groups such as butenyl groups;
straight or branched C3-C30 perhalogenated alkenyl groups such as perfluoroalkenyl groups and perchloroalkenyl groups such as perfluorovinyl groups, perfluoroallyl groups and perfluorobutenyl groups;
a C3-C30 cycloalkyl group (C _n H _2n-1 : n=3-30);
C3-C30 perhalogenated cycloalkyls such as perfluorocycloalkyl groups (C _n F _2n-1 : n=3-30) and perchlorocycloalkyl groups (C _n Cl _2n-1 : n=3-30) group;
C3-C30 cycloalkenyl groups such as a cyclopentenyl group and a cyclohexenyl group;
C3-C30 perhalogenated cycloalkenyl groups such as perfluorocycloalkenyl groups and perchlorocycloalkenyl groups; and C3-C30 alkynyl groups, and halogeno groups (eg, F, Cl, etc., preferably F) can have one or more substituents.
In this specification, two groups of substituents, Group (G1) and Group (G), are shown, but Group (G) is a more concise description of Group (G1) and is substantially the same. is.

^Further , the group (G1 ) are, for example, deuterium atoms, halogeno groups (F, Cl, Br and I), hydroxyl groups, nitro groups, sulfonyl groups, cyano groups, silyl groups, phosphonic acid groups, diazo groups, methoxy groups, It may be substituted with a substituent such as an amide group, a carboxyl group, and a mercapto group.

The group (G1) which can be selected as a substituent of the C1-C30 alkyl group, the C3-C30 cycloalkyl group, the C1-C30 perhalogenated alkyl group and the C3-C30 perhalogenated cycloalkyl group of ^A2 is , considering the stability and emission intensity of the rare earth metal complex or the transparent solid carrier containing the same, C1 to C30 alkyl groups, C1 to C30 perhalogenated alkyl groups, aromatic groups, perhalogenated aromatic groups and It preferably contains a heteroaromatic group and a perhalogenated heteroaromatic group, more preferably a C1-C30 alkyl group, a C1-C30 perfluoroalkyl group, and a C3-C30 cycloalkyl group. , butyl, dodecyl and cyclohexyl groups are particularly preferred.

In addition, the C1-C30 alkyl group, C3-C30 cycloalkyl group, C1-C30 perhalogenated alkyl group and C3-C30 perhalogenated cycloalkyl group of A ² are C An ether structure, an ester structure and/or a tertiary amine may be included by inserting one or more of -O-, -COO-, -N< between -C single bonds.
Furthermore, ^A2 can have unsaturated groups such as alkenyl groups as described above, as long as it does not form a conjugated system with the azomethine group.
Even more preferably, A2 is selected from hydrogen, deuterium, methyl groups, trifluoromethyl groups and cyclopropyl groups.

The ligand of chemical formula (I) has two pairs of A ¹ and an azomethine group, for example, as shown in the chemical structure of chemical formula (IV), only one A ¹ forms a coordination bond with a rare earth metal For example, both A ¹ may form coordinate bonds with the same rare earth metal, or form coordinate bonds with different rare earth metals, as shown in the chemical structures of formulas (V) and (VI). may be formed.
The ligand of formula (II) has a pair of A ¹ and an azomethine group, and one A ¹ forms a coordination bond with a rare earth metal, for example, as shown in the chemical structure of formula (VII) .

The chemical structures of formulas (IV) and (VII) are mononuclear complexes containing one rare earth metal atom, and the chemical structures of chemical formulas (V) and (VI) are dinuclear complexes containing two or more rare earth metal atoms. could be. The chemical structure of chemical formula (V) represents a cyclic dinuclear complex formed by cyclically linking multiple ligands through multiple rare earth metals, and the chemical structure of chemical formula (VI) represents multiple rare earth metals. A chain-like dinuclear complex formed by linking multiple ligands in a chain via a metal.

In the ligand of formula (I), the nitrogen atoms of the two azomethine groups are linked by a linking group ^A3 (see, for example, formulas (I), (IV)-(VI)).
A ³ is selected from C2-C30 alkylene groups (—C _n H _2n —, where n=2-30, preferably n=4-18, more preferably n=4-12).

^A3 can have one or more substituents selected from the above group (G1) and halogeno groups (eg, F, Cl, etc., preferably F).

Furthermore, substituents included in the group (G1) that can be selected as the substituent of ^A3 include, for example, deuterium atom, halogeno groups (F, Cl, Br and I), hydroxyl group, nitro group, sulfonyl group, cyano may be substituted with substituents such as groups, silyl groups, phosphonic acid groups, diazo groups, methoxy groups, amide groups, carboxyl groups, and mercapto groups.

Group (G1) that can be selected as a substituent of ^A3 is a C1 to C30 alkyl group, C1 to C30 perhalogen, considering the stability and emission intensity of the rare earth metal complex or the transparent solid support containing the same. Alkyl groups, aromatic groups, perhalogenated aromatic groups and heteroaromatic groups and perhalogenated heteroaromatic groups are preferred, and alkyl groups having 1 to 30 carbon atoms and perfluoroalkyl groups having C1 to C30 , and C3-C30 cycloalkyl groups, particularly preferably butyl, dodecyl and cyclohexyl groups.

In addition, A ³ is an ether structure, an ester structure, and / by inserting one or more of -O-, -COO-, -N< Or it may contain a tertiary amine.
Furthermore, ^A3 can have unsaturated groups such as alkenyl groups as described above, as long as they do not form a conjugated system with the azomethine group.

In ligands of Formula (II), the nitrogen atom of one azomethine group can have a substituent A ⁴ (see, eg, Formulas (II) and (VII)).
A ⁴ is selected from C1-30 alkyl groups (-C _n H _2n+1 , where n=1-30, preferably n=1-18, more preferably n=4-12).
A ⁴ can have one or more substituents selected from the group (G1) described for A ³ above as well as halogeno groups (eg F, Cl etc., preferably F). :

Furthermore, substituents included in the group (G1) that can be selected as ^A4 are, for example, deuterium atoms, halogeno groups (F, Cl, Br and I), hydroxyl groups, nitro groups, sulfonyl groups, cyano groups, silyl groups , a phosphonic acid group, a diazo group, a methoxy group, an amide group, and a mercapto group.

Group (G1) that can be selected as A ⁴ is a C1-C30 alkyl group, a C1-C30 perhalogenated alkyl group, considering the stability and emission intensity of the rare earth metal complex or the transparent solid support containing it, It preferably contains an aromatic group, a perhalogenated aromatic group and a heteroaromatic group and a perhalogenated heteroaromatic group, an alkyl group having 1 to 30 carbon atoms, a C1 to C30 perfluoroalkyl group, and a C3 to It more preferably contains a C30 cycloalkyl group, and particularly preferably contains a butyl group, a dodecyl group and a cyclohexyl group.

A ⁴ may also contain an ether structure and/or an ester structure by inserting one or a plurality of —O— or —COO— between the C—C single bonds at arbitrary positions therein.

Both the hydroxyl group or thiol group (A ¹ ) and the azomethine group (-CA ² =N-) in the ligands of the above chemical formulas (I) to (II) and the chemical structures of the chemical formulas (IV) to (VII) For ligands having A ¹ and a benzene ring having both an azomethine group and a naphthalene ring that can be formed are further selected from the above group (G1) and halogeno groups (e.g., F, Cl, etc., preferably F) It can have one or more substituents.

Furthermore, the substituents included in the above-described group (G1) that the benzene ring and naphthalene ring that can be formed may have include, for example, deuterium atoms, halogeno groups (F, Cl, Br and I), hydroxyl groups, nitro groups , a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, a methoxy group, an amide group, and a mercapto group.

Considering the stability and emission intensity of the rare earth metal complex or the transparent solid support containing the same, the group (G1) containing substituents that the benzene ring and the naphthalene ring may have includes C1 to C30 alkyl groups, C1 to C30 It preferably contains a perhalogenated alkyl group, an aromatic group, a perhalogenated aromatic group and a heteroaromatic group and a perhalogenated heteroaromatic group, an alkyl group having 1 to 30 carbon atoms, a C1 to C30 per Fluoroalkyl groups and C3-C30 cycloalkyl groups are more preferred, and butyl, dodecyl and cyclohexyl groups are particularly preferred.

The β-diketonato ligand of chemical formula (III) included in the chemical structures of chemical formulas (IV) to (VII) above will now be described.
β-diketonato ligands are monovalent anions that can coordinate to rare earth metals with two oxygen atoms.
A metal complex according to an embodiment of the present invention has a rare earth metal coordinated with a β-diketonato ligand together with the above ligand having both a hydroxyl group or a thiol group and an azomethine group.

The β-diketonato ligand has two X's, which may be the same or different.
X is the following group (G1):
aromatic groups such as phenyl, naphthyl and biphenyl groups;
Perhalogenated aromatic groups such as a perfluorophenyl group, a perfluoronaphthyl group, a perfluorobiphenyl group, a perchlorophenyl group, a perchloronaphthyl group, and a perchlorobiphenyl group;
a heteroaromatic group containing at least one heteroatom selected from N, O, S, etc. in the ring;
linear or branched C1-C30 alkyl group (C _n H _2n+1 : n=1-30);
Linear or branched C1-C30 perhalogenated alkyl such as perfluoroalkyl group (C _n F _2n+1 : n=1 to 30) and perchloroalkyl group (C _n Cl _2n+ 1 : n=1 to 30) group;
straight or branched C3-C30 alkenyl groups such as butenyl groups;
straight or branched C3-C30 perhalogenated alkenyl groups such as perfluoroalkenyl groups and perchloroalkenyl groups such as perfluorovinyl groups, perfluoroallyl groups and perfluorobutenyl groups;
a C3-C30 cycloalkyl group (C _n H _2n-1 : n=3-30);
C3-C30 perhalogenated cycloalkyl such as perfluorocycloalkyl group (C _n F _2n-1 : n=3-30) and perchlorocycloalkyl group (C _n Cl _2n-1 : n=3-30) group;
C3-C30 cycloalkenyl groups such as a cyclopentenyl group and a cyclohexenyl group;
C3-C30 perhalogenated cycloalkenyl groups such as perfluorocycloalkenyl groups and perchlorocycloalkenyl groups; and C3-C30 alkynyl groups.

Furthermore, substituents included in the above group (G1) that can be selected as X are, for example, deuterium atoms, halogeno groups (F, Cl, Br and I), hydroxyl groups, nitro groups, amino groups, sulfonyl groups, cyano may be substituted with substituents such as radicals, silyl groups, phosphonic acid groups, diazo groups, and mercapto groups.

Group (G1) that can be selected as X preferably includes a perfluoroalkyl group (C _n F _2n+1 : n=1 to 30), a phenyl group, a naphthyl group, a phenanthryl group, and a perfluoroalkyl group (C _n F _2n+1 : n=1 to 6), a phenyl group and a naphthyl group, and particularly preferably a perfluoroalkyl group (C _n F _2n+1 : n=1 to 3), a phenyl group and a naphthyl group.

Z of the β-diketonato ligand preferably contains a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a methyl group, an ethyl group, a phenyl group, a hydrogen atom or a deuterium atom. It is particularly preferable to contain a hydrogen atom or a fluorine atom.

La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy as rare earth elements (for example, Ln in chemical formulas (IV) to (VII)) for the rare earth metal complex of the embodiment of the present invention , Ho, Er, Tm, Yb and Lu can be exemplified, and Eu, Sm and Dy are preferred. These rare earth elements can be used individually or in combination of 2 or more types.

The rare earth metal complexes of embodiments of the present invention may further contain other ligands. Other ligands are not particularly limited as long as the rare earth metal complex targeted by the embodiment of the present invention can be obtained. Anions and the like selected from compound ions can be exemplified. Other ligands are designated Y, for example, in formulas (IV)-(VII). Other ligands are preferably selected from carbonate, sulfate and trifluoromethanesulfonic acid.

For rare earth metal complexes of embodiments of the present invention comprising chemical structures of formulas (IV)-(VII):
n1, which indicates the positive charge of the rare earth element, is 2 or 3, preferably 3;
n2, which indicates the number of β-diketonato ligands, is 1-3.
n3 representing the number of other ligands is any one of 0-2.
n4 representing the number of ligands having an azomethine group is 1-3.
The coordination number of rare earth metals is 3-11.
It is preferable that n2 and n3 be a combination of n2+n3=3.
Furthermore, n2 is more preferably 3 and n3 is more preferably 0.
n4 is more preferably 2.
n5, which indicates the number of cyclically continuous ligands, is preferably an integer of 2 or more, more preferably 2-8.
n6, which indicates the number of chained ligands, is preferably an arbitrary integer, more preferably 3 or more.

The present embodiment can provide a novel trivalent rare earth complex having both a ligand having a hydroxyl group or a thiol group and an azomethine group (Schiff base) and a β-diketonato ligand.
The new trivalent rare earth complex can preferably be used as a wavelength conversion member, and more preferably can absorb and emit light in the ultraviolet to blue light region.
Further, the trivalent rare earth metal complex more preferably has a broader excitation wavelength region in the visible light region, a higher absorbance, a lower reflectance, and a higher external quantum efficiency.
The rare earth metal complex of the embodiment of the present invention provides a novel rare earth metal complex, and by changing the structure of the ligand and / or the type of rare earth atom, etc., can change the absorption wavelength region, The emission wavelength range can be varied. Therefore, the rare earth metal complexes of the embodiments of the present invention can provide wavelength conversion materials with various new properties.

The rare earth metal complexes of the embodiments of the present invention (more specifically, for example, complexes containing chemical structures represented by chemical formulas (IV) to (VII)) are subject to special restrictions as long as they can be obtained. no.
The rare earth metal complexes of the embodiments of the present invention correspond to, for example, rare earth metal salts (e.g., chlorides and acetates of rare earth metals, etc.) and the above-described β-diketonato ligands, as shown in the examples below. It can be obtained by reacting a β-diketone with a ligand having both a hydroxyl group or a thiol group and an azomethine group. The order of reacting the rare earth metal salt with these ligands, reaction conditions such as reaction temperature, reaction time, reaction concentration, etc., can be appropriately selected.

When producing a Z=D complex of a β-diketonato ligand (see, for example, chemical formula (III)), a Z=H complex (see, for example, chemical formulas (IV) to (VII)) is produced, Z=H can then be converted to Z=D to give the Z=D complex.
The deuterated complex (Z is heavy A complex that is a hydrogen atom D) can be obtained.

Such deuteration agents include, for example, protic compounds containing deuterium, specifically heavy water; deuterated alcohols such as deuterated methanol and deuterated ethanol; hydrogen chloride; Including alkali, etc.
Base agents and additives such as trimethylamine and triethylamine may be added to facilitate the deuterium substitution reaction.

The deuterium substitution reaction can be performed by mixing the rare earth metal complex of the embodiment of the present invention and a deuteration agent, and an aprotic solvent may be added during the reaction.
Aprotic solvents include, for example, ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as diethyl ether and tetrahydrofuran; halogen solvents such as chloroform and methylene chloride; DMSO and DMF; Solvents in which the rare earth metal complexes of the present embodiments are soluble are preferred.

The deuteration agent is preferably used in an amount of about 1 to 100 parts by weight with respect to the total amount (1 part by weight) of the rare earth metal complex of the embodiment of the present invention during the deuterium substitution reaction. , more preferably in an amount of about 1 to 20 parts by weight.

The method for mixing the rare earth metal complex and the deuteration agent according to the embodiment of the present invention is not particularly limited as long as a deuterated complex can be obtained. As such a mixing method, for example, at a temperature of from room temperature to 150° C., preferably from 30° C. to 100° C., with stirring as necessary, for 0.1 to 100 hours, preferably from 0.1 to 20 hours. A method of time mixing can be exemplified.
After stirring, deuterated rare earth metal complexes (Z=deuterium D) of embodiments of the present invention can be obtained by distilling off the deuteration agent and solvent.
If desired, it can be further purified using methods such as recrystallization, column chromatography and sublimation.

The rare earth metal complexes of the embodiments of the present invention can be used, for example, as various optical functional materials such as luminescence aids, optical lenses, fluorescent probes, and security inks.
Furthermore, by incorporating the rare earth metal complex of the embodiment of the present invention into a transparent solid carrier, it can be similarly used for various optical functional materials. Incorporation of a rare earth metal complex into the transparent solid carrier is preferable because it improves ease of handling, stability, moldability, and the like.
Accordingly, the present invention provides a transparent solid carrier for optical functional material containing the rare earth metal complex of the embodiment of the present invention, and a transparent solid carrier for optical functional material comprising a transparent solid carrier containing the rare earth metal complex of the embodiment of the present invention. A method for producing a solid support is provided.

The transparent solid support of the embodiment of the invention is not particularly limited as long as it is transparent and solid and can be used as a support for the rare earth metal complex of the embodiment of the invention. For example, transparent polymer matrices, transparent glasses, and the like can be used.

Examples of the transparent polymer matrix include polymethyl methacrylate (PMMA), fluorine-containing polymethacrylate, polyacrylate, fluorine-containing polyacrylate, polystyrene, polyolefin (e.g., polyethylene, polypropylene, polybutene, etc.), fluorine-containing polyolefin, polyvinyl ether, fluorine-containing Polyvinyl ether, polyvinyl acetate, polyvinyl chloride, copolymers thereof, cellulose, polyacetal, polyester, polycarbonate, epoxy resin, polyamide resin, polyimide resin, polyurethane, Nafion, petroleum resin, rosin, silicon resin, etc. can be exemplified. .
Polymethyl methacrylate, fluorine-containing polymethacrylate, polyacrylate, fluorine-containing polyacrylate, polystyrene, polyolefin, polyvinyl ether, copolymers thereof, silicon resin, epoxy resin, and the like are preferably used as the transparent polymer matrix.
These can be used individually or in combination of 2 or more types.

The rare earth metal complex of the embodiment of the present invention preferably has a reflectance of 50% or less, more preferably 40 to 1%, and particularly preferably 30 to 1% for incident light of 450 nm. .
The rare earth metal complex of the embodiment of the present invention preferably has a reflectance of 60% or more, more preferably 70 to 120%, and particularly preferably 80 to 120% for incident light of 550 nm. .
Here, the reflectance is a relative value with the reflectance of calcium phosphate being 100% (reference).

The rare earth metal complex of the embodiment of the present invention preferably has an external quantum efficiency of 5% or more, more preferably 5 to 99%, even more preferably 10 to 99%, and 30 to 99% is particularly preferred.
The external quantum efficiency is a value when excited with excitation light of 380 nm and 450 nm.

Since the reflectance of the rare earth metal complexes of the embodiments of the present invention and the transparent solid support comprising the same for incident light of 450 nm can be lower than the reflectance of the conventional rare earth metal complexes for incident light of 450 nm, the conventional rare earth metal complexes can have higher wavelength conversion efficiency for incident light of 450 nm compared to . Further, by using the rare earth metal complex of the embodiment of the present invention, a light-emitting device with more preferably high luminous efficiency can be obtained.

A light-emitting device according to an embodiment of the present invention is constructed by combining a rare earth metal complex according to an embodiment of the present invention or a transparent solid carrier containing the same with a light-emitting diode or laser diode.
The rare earth metal complex of the embodiment of the present invention or a transparent solid carrier containing the same can be applied to the upper surface (light exit surface) of the light guide plate, the side surface (light incident surface of the light emitting diode), and the inside of the cup of the light emitting device, as with conventional phosphors. Also, it can be placed in a resin or the like that seals the light-emitting diode.

The light-emitting diode or laser diode preferably emits light at a wavelength approximately matching the peak wavelength of the excitation spectrum corresponding to the ff transition of the central ion of the rare earth metal complex of the embodiment of the present invention or the absorption of the ligand. . As a light emitting diode or laser diode, for example, a nitride semiconductor light emitting device including a nitride semiconductor layer containing In as a light emitting layer can be used. The emission peak wavelength of this nitride semiconductor light-emitting device can be adjusted by changing the In content of the light-emitting layer.

Furthermore, as shown in Examples below, the rare earth metal complexes of the embodiments of the present invention can more preferably exhibit an excitation spectrum in a wide region from ultraviolet to visible. In such a case, a light-emitting device can be constructed using a plurality of light-emitting elements corresponding to respective wavelengths.

The light-emitting device according to the embodiment of the present invention can be used, for example, as a general lighting device, a signal device, a display device, and the like. More specifically, for example, automobile brake lights, door indicator lights, decorative panels installed in stores, etc., backlights and sidelights for display devices such as personal computers, mobile terminals, mobile phones, smartphones, tablets, etc. can be exemplified.

Embodiments according to the present invention will be described below using examples and comparative examples, but these examples are for describing the embodiments according to the present invention, and do not limit the present invention in any way.

Raw materials and the like used to synthesize the complexes of Examples and Comparative Examples are shown below.
A ligand (A) having a hydroxyl group or a thiol group and an azomethine group
(a1) N,N′-bis(salicylidene)ethylenediamine (H ₂ salen) [HO-C ₆ H ₄ -CH=N-(CH ₂ ) ₂ -N=CH-C ₆ H ₄ -OH] (benzene ring are both ortho-substitutions)
(a2) N,N'-bis(salicylidene)1,4-butylene diamine (H ₂ 1,4-butylene diamine) [HO-C ₆ H ₄ -CH=N-(CH ₂ ) ₄ -N=CH-C ₆ H ₄ —OH] (both benzene rings are ortho-substituted)
(a3) N,N'-bis(salicylidene)1,6-hexylenediamine (H ₂ 1,6-salhxn) [HO-C ₆ H ₄ -CH=N-(CH ₂ ) ₆ -N=CH- C ₆ H ₄ —OH] (both benzene rings are ortho-substituted)
(a4) N,N′-bis(p-hydroxyphenylacetylidene)1,4-butylenediamine (H ₂ 1,4-acebn) [HO—C ₆ H ₄ —C(CH ₃ )=N—(CH ₂ ) ₄ -N=C( _CH3 ) _{-C6H4 -} OH] (both benzene rings are ortho substituted)
(a5) N,N'-bis(2-hydroxynaphthyl-1-methylidene)1,4-butylenediamine (H ₂ 1,4-napbn) [HO-C ₁₀ H ₆ -CH=N-(CH ₂ ) ₄ -N=CH- _{C10H6 -} OH]

β-diketone (B)
(b1) hexafluoroacetylacetone (hfa) [CF ₃ —CO—CH ₂ —CO—CF ₃ ]
A β-diketonato ligand that is a monovalent anion is also referred to as "hfa- ^" .
(b2) Benzoyltrifluoroacetone (btfa) [CF ₃ —CO—CH ₂ —CO—C ₆ H ₅ ]
A β-diketonato ligand that is a monovalent anion is also referred to as “btfa ⁻ ”.

Metal salt (C)
(c1) europium acetate [Eu( _CH3COO ) ₃ ( _H2O )]
(c2) Europium chloride [ _EuCl3 ( _H2O ) ₆ ]
Other (D)
bis[(2 _- diphenylphosphoryl)phenyl]ether (DPEPO) _[ (C6H5 _{) 2P} (=O) _{-C6H4 - OC6H4 -} P(=O)( _C6H5 ) ₂ ]

Example 1: Synthesis of a complex containing europium co-coordinated with H ₂ salen and ^hfa- (c1) Europium acetate [Eu(CH ₃ COO) ₃ (H ₂ O): 0.5 g] was dissolved in 50 mL of ethanol. Ta. (b1) Hexafluoroacetylacetone (hfa) [CF ₃ --CO--CH ₂ --CO--CF ₃ : 0.9 g] was added and stirred at room temperature for 1 hour.
(a1) N,N'-bis(salicylidene)ethylenediamine (H ₂ salen) [HO-C ₆ H ₄ -CH=N-(CH ₂ ) ₂ -N=CH-C ₆ H ₄ -OH: 0.77 g ] (both benzene rings are ortho-substituted) and stirred at room temperature for 24 hours. After stirring, the precipitated solid was filtered. Ethanol was removed by vacuum distillation to give a yellow product. Recrystallization was performed using a mixed solvent of ethanol and dichloromethane to obtain the complex of Example 1.

Structural analysis of the complex of Example 1 was carried out by single crystal X-ray structural analysis. The resulting ORTEP diagram is shown in FIG. From FIG. 3, the complex of Example 1 has a chemical formula of Eu(H ₂ salen) ₂ (hfa ⁻ ) ₂ (CH ₃ COO ⁻ ), where one Eu ³⁺ in the center has one CH ₃ COO ⁻ It was found to coordinate with two oxygens, two hfa ⁻ coordinated with two oxygens each, and two H ₂ salen coordinated with one oxygen each. In other words, it was confirmed that β-diketonato and phenol having an azomethine group were coordinated to europium at the same time. A total of 8 oxygen atoms are coordinated and are considered to be 8-coordinated. It is believed that the two monovalent anions β-diketonato balance the charge with the monovalent acetate ion. In the complex of Example 1, one hydroxyl group of H ₂ salen is coordinated to Eu ³⁺ to form a simple mononuclear complex.
The results of elemental analysis supported the results of single crystal X-ray structure analysis as follows.
Elemental analysis: calculated C 45.49% H 3.21% N 4.82%, measured C 45.70% H 3.17% N 4.79%

Example 2: Synthesis of a complex containing europium co-coordinated with H ₂ 1,4-salbn and ^hfa- (c1) Europium acetate [5.0 g] was dissolved in 40 mL of distilled water. (b1) Hexafluoroacetylacetone (hfa) [8.1 g] was added and stirred at room temperature for 4 hours.
After stirring, the precipitated solid was filtered. Distilled water was removed by distillation under reduced pressure to obtain a white product. 1.62 g of the white product obtained was dissolved in 40 ml diethyl ether.
(a2) N,N'-(salicylidene)1,4-butanediamine (H ₂ 1,4-salbn) [HO-C ₆ H ₄ -CH=N-(CH ₂ ) ₄ -N=CH-C ₆ H ₄ —OH: 1.19 g] (both benzene rings are ortho-substituted) was added and stirred at room temperature for 24 hours. The precipitated solid was filtered. Diethyl ether was removed by distillation under reduced pressure to give a yellow product. A complex of Example 2 was obtained by recrystallization using a mixed solvent of tetrahydrofuran and hexane.

Structural analysis of the complex of Example 2 was performed by single crystal X-ray structural analysis. The resulting ORTEP diagram is shown in FIG. From FIG. 4, the complex of Example 2 has the chemical formula of Eu ₂ (H ₂ 1,4-salbn) ₂ (hfa ⁻ ) ₄ (CH ₃ COO ⁻ ) ₂ , where each of the two Eu has one It was found that the acetate ion is coordinated with two oxygens, two ^hfa- are coordinated with two oxygens each, and two H ₂ 1,4-salbn are coordinated with one oxygen each. Ta. That is, it was confirmed that β-diketonato and phenol having an azomethine group were coordinated to each Eu at the same time. Each Eu is coordinated by 8 oxygen atoms and is considered octacoordinated. For each Eu, two monovalent anions, β-diketonates, are believed to balance the charge together with the monovalent acetate ion. In the complex of Example 2, two hydroxyl groups at both ends of H ₂ 1,4-salbn are coordinated with different Eu to form a multinuclear cyclic structure complex.
The results of elemental analysis supported the results of single crystal X-ray structure analysis as follows.
Elemental analysis: calculated C 39.10% H 2.73% N 3.04%, measured C 39.26%, H2.66%, N2.94%

Example 3: Synthesis of a complex containing europium co-coordinated with H ₂ 1,6-salhxn and ^hfa- (c1) Europium acetate [5.0 g] was dissolved in 40 mL of distilled water. (b1) Hexafluoroacetylacetone (hfa) [8.1 g] was added and stirred at room temperature for 4 hours.
After stirring, the precipitated solid was filtered. Distilled water was removed by distillation under reduced pressure to obtain a white product. 0.81 g of the white product obtained was dissolved in 40 ml diethyl ether.
(a3) N,N'-bis(salicylidene)1,6-hexanediamine (H ₂ 1,6-salhxn) [HO-C ₆ H ₄ -CH=N-(CH ₂ ) ₆ -N=CH-C ₆ H ₄ -OH: 0.65 g] (both benzene rings are ortho-substituted) was added and stirred at room temperature for 24 hours.
The precipitated solid was filtered. Diethyl ether was removed by distillation under reduced pressure to give a yellow product. Recrystallization was performed using a mixed solvent of dichloromethane and ethanol to obtain the complex of Example 3.

Structural analysis of the complex of Example 3 was carried out by single crystal X-ray structural analysis. The resulting ORTEP diagram is shown in FIG. From FIG. 5, the complex of Example 3 has the formula [Eu(H ₂ 1,6-salhxn)(hfa ⁻ ) ₂ (CH ₃ COO ⁻ )]n, where each Eu has one acetate ion coordinated by two oxygens, two ^hfa- coordinated by two oxygens each, and two H ₂ 1,6-salhxn coordinated by one oxygen each. That is, it was confirmed that β-diketonato and phenol having an azomethine group were coordinated to each Eu at the same time. Each Eu is coordinated by 8 oxygen atoms and is considered octacoordinate. For each Eu, two monovalent anions, β-diketonates, are believed to balance the charge together with the monovalent acetate ion. In the complex of Example 3, two hydroxyl groups at both ends of H ₂ 1,6-salhxn are coordinated with different Eu to form a complex with a polynuclear chain polymer structure. The Ortep diagram of FIG. 5 shows the structure of approximately three repeat units for the complex of the linear polymer structure of Example 3.
The results of elemental analysis supported the results of single crystal X-ray structure analysis as follows.
Elemental analysis: calculated C 40.48% H 3.08% N 2.95%, measured C 40.34%, H2.96%, N2.88%

Example 4: Synthesis of a complex containing europium co-coordinated by H ₂ 1,4-salbn and ^btfa- (c2) Europium chloride [EuCl ₃ (H ₂ O) ₆ : 2.2 g] was dissolved in 30 mL of methanol. Ta. (b2) Benzoyltrifluoroacetone (btfa) [CF ₃ —CO—CH ₂ —CO—C ₆ H ₅ : 3.9 g] was added, adjusted to pH 7 with an aqueous ammonia solution, and stirred at room temperature for 4 hours. After stirring, 300 ml of pure water was added, and the mixture was stirred for 12 hours, and the precipitated solid was filtered. Distilled water was removed by distillation under reduced pressure to obtain a white product. 1.67 g of the white product obtained was dissolved in 40 ml diethyl ether.
(a2) 0.60 g of H ₂ 1,4-salbn (both benzene rings are ortho-substituted) was added and stirred at room temperature for 24 hours. The precipitated solid was filtered. Diethyl ether was removed by distillation under reduced pressure to give a yellow product. The complex of Example 4 was obtained by recrystallization with a diethyl ether solvent.

Structural analysis of the complex of Example 4 was carried out by single crystal X-ray structural analysis. The resulting ORTEP diagram is shown in FIG. From FIG. 6, the complex of Example 4 has the chemical formula of Eu ₄ (H ₂ 1,4-salbn) ₄ (btfa ⁻ ) ₁₂ , where each Eu has 3 btfa ⁻ coordinated with two oxygens each. It was found that two H ₂ 1,4-salbns were coordinated with one oxygen each. That is, it was confirmed that β-diketonato and phenol having an azomethine group were coordinated to each Eu at the same time. Each Eu is coordinated by 8 oxygen atoms and is considered octacoordinated. For each Eu, three monovalent anions, β-diketonates, are believed to balance the charge. In the complex of Example 4, two hydroxyl groups at both ends of H ₂ 1,4-salbn are coordinated with different Eu to form a tetranuclear cyclic (tetrahedral) complex. The Ortep diagram of FIG. 6 shows that the two tetranuclear ring structure complexes of Example 4 are side by side.
The results of elemental analysis supported the results of single crystal X-ray structure analysis as follows.
Elemental analysis: calculated C 52.71% H 3.50% N 2.56%, measured C 52.49%, H 3.36%, N 2.50%

Example 5: Synthesis of a complex containing europium co-coordinated by H ₂ 1,4-acebn and ^btfa- (c2) Europium chloride [2.2 g] was dissolved in 30 mL of methanol. (b2) Benzoyltrifluoroacetone (btfa) [3.9 g] was added, adjusted to pH 7 with an aqueous ammonia solution, and stirred at room temperature for 4 hours. After stirring, 300 ml of pure water was added, and the mixture was stirred for 12 hours, and the precipitated solid was filtered. Distilled water was removed by distillation under reduced pressure to obtain a white product.
1.68 g of the white product obtained were dispersed in 50 ml of dichloromethane.
(a4) N,N′-bis(hydroxyphenylacetylidene)1,4-butanediamine (H ₂ 1,4-acebn) [HO—C ₆ H ₄ —C(CH ₃ )=N—(CH ₂ ) ₄ -N=C(CH ₃ )-C ₆ H ₄ -OH: 0.65 g] (both benzene rings are ortho-substituted) and stirred at room temperature for 4 hours. The precipitated solid was filtered. Dichloromethane was removed by evaporation under reduced pressure to give a yellow product. The complex of Example 5 was obtained by washing with a cold ethanol solvent and removing the ethanol by distillation under reduced pressure.

Example 6: Synthesis of complex containing europium coordinated by H ₂ 1,4-napbn and ^btfa- (c2) Europium chloride [2.2 g] was dissolved in 30 mL of methanol. (b2) Benzoyltrifluoroacetone (btfa) [3.9 g] was added, adjusted to pH 7 with an aqueous ammonia solution, and stirred at room temperature for 4 hours. After stirring, 300 ml of pure water was added, and the mixture was stirred for 12 hours, and the precipitated solid was filtered. Distilled water was removed by distillation under reduced pressure to obtain a white product.
1.68 g of the white product obtained were dispersed in 50 ml of dichloromethane.
(a5) N,N'-bis(hydroxynaphthylmethylidene) 1,4-butanediamine (H ₂ 1,4-napbn) [HO-C ₁₀ H ₆ -CH=N-(CH ₂ ) ₄ -N= CH—C ₁₀ H ₆ —OH: 0.40 g] (both benzene rings are ortho-substituted) was added and stirred at room temperature for 4 hours. The precipitated solid was filtered. Dichloromethane was removed by evaporation under reduced pressure to give a yellow product. The yellow product was washed with cold ethanol, and the ethanol was removed by distillation under reduced pressure to obtain the complex of Example 6.

Comparative Example 1: Synthesis of Eu(hfa ⁻ ) ₃ (DPEPO) complex (c1) europium acetate, (b1) hexafluoroacetylacetone (hfa) and bis[(2-diphenylphosphoryl)phenyl]ether (hereinafter also referred to as “DPEPO”) ) [(C ₆ H ₅ ) ₂ P(=O)-C ₆ H ₄ -O-C ₆ H ₄ -P(=O)(C ₆ H ₅ ) ₂ ], described in Non-Patent Document 1 The complex of Comparative Example 1 was synthesized based on the method described above. The structure of the complex of Comparative Example 1 was confirmed by elemental analysis, single crystal X-ray structure analysis, and the like.

The complexes of Examples 1-6 each contain a rare earth metal coordinated with a ligand having both a hydroxyl or thiol group and an azomethine group and a β-diketonato ligand.
It was found that the complexes of Examples 1 to 6 all absorb light in the wavelength range from ultraviolet light to visible light, generate light with a longer wavelength than the absorbed light, and can function as a wavelength conversion material. .
The complexes of Examples 1-6 absorbed blue light and emitted light with wavelengths longer than blue.
Among them, the emission properties of the complexes of Examples 1-4 were superior, as further explained below.

7 shows excitation spectra of the complexes of Examples 1 to 4 and Comparative Example 1. FIG. The absorbance (% of photons) (vertical axis) is plotted against the wavelength of excitation light (horizontal axis).
The complexes of Examples 1 to 4 have broad absorption from the ultraviolet region (300 nm) to the visible light region (500 nm). These absorptions are due to β-diketonato ligands and ligands with azomethine groups.
On the other hand, in the complex of Comparative Example 1, the absorption decreased from 350 nm and became 10% or less at 450 nm.

FIG. 8a shows the emission spectra of the complexes of Examples 1 to 4 and the complex of Comparative Example 1, and FIG. 8b shows a partially enlarged emission spectrum of FIG. 8a. Emission intensity is plotted against wavelength (horizontal axis). FIG. 8a shows the emission intensity for wavelengths 500-750 nm, and FIG. 8b shows the portion of the emission intensity for wavelengths 600-640 nm in FIG. 8a. Comparing the spectra of the complexes of Examples 1 to 4 with the spectrum of the complex of Comparative Example 1, a significant difference was observed in the spectral shape at 615 nm. In the complexes of Examples 1 to 4, compared with the complex of Comparative Example 1, the peak intensity near 615 nm was remarkably increased.
7, 8a, and 8b, the complexes of Examples 1 to 4 can emit more light than the complex of Comparative Example 1 even when excited by excitation light of around 450 nm.

External quantum efficiency of the complexes of Examples 1-4 and Comparative Example 1 with 380 nm excitation light and 450 nm excitation light, and the reflectance of the complexes of Examples 1-4 and Comparative Example 1 for incident light of 450 nm and 550 nm are shown in Table 1.
Here, the external quantum efficiency is defined by the following formula (1).
In the quantum efficiency measurement, the sample to be measured is measured under the condition that the sample is thick enough not to transmit the excitation light, and the quantum efficiency is calculated with respect to the emission quantum number emitted from the sample surface.
The external quantum efficiency (hereinafter referred to as EQE) is defined by the following formula (1), where E(λ) is the excitation light spectrum of the sample and P(λ) is the emission spectrum of the sample.

［式（１）において、λ１、λ２は励起光および試料の発光スペクトルが過不足なく含まれる波長の範囲であれば、任意の波長であってよい。］

[In formula (1), λ1 and λ2 may be arbitrary wavelengths as long as they are in the range of wavelengths in which the excitation light and the emission spectrum of the sample are included in just the right amount. ]

FIG. 9 shows reflection spectra of the rare earth complexes of Examples 1 to 4 and the rare earth complex of Comparative Example 1. FIG. Reflectance is plotted against wavelength (horizontal axis). Here, the reflectance is a relative value with the reflectance of calcium phosphate being 100% (reference).
Comparing the spectra of the complexes of Examples 1 to 4 with the spectrum of the complex of Comparative Example 1, a significant difference was observed in the spectral shapes at wavelengths of 500 nm or less. The complexes of Examples 1 to 4 had a reflectance of 10% or less for light of 400 to 430 nm, but the reflectance increased from 440 nm and exceeded 80% at 500 nm. The complex of Comparative Example 1 had a reflectance of about 80% for light of 400 nm and about 90% for light of 500 nm. Therefore, the complexes of Examples 1 to 4 exhibit low reflectance at wavelengths below 500 nm, ie, are capable of absorbing light at wavelengths below 500 nm.

Comparing the external quantum efficiencies of the complexes of Examples 1 to 4 with the external quantum efficiency of the complex of Comparative Example 1, the external quantum efficiency at 380 nm of Example 2 is higher than that of Examples 1 and 3. The external quantum efficiency of ∼4 is comparable to that of Comparative Example 1.
Compared with the reflectance at 450 nm of Comparative Example 1, the reflectance at 450 nm in Examples 1 to 4 is low, so it is difficult to excite in Comparative Example 1 with light in the visible light region. It can be seen that the complex of 4 can be excited by light in the visible region.
Therefore, the complex of Comparative Example 1 can be used by being excited by ultraviolet light, while the complexes of Examples 1 to 4 can be used by being further excited by light in the visible region.

Production of Transparent Solid Carrier and Light-Emitting Device and Evaluation of Luminescent Properties The complex of Example 2 was dispersed in a silicone resin and cured by heating to obtain a transparent solid carrier.
A light-emitting device was obtained by mounting this transparent solid carrier on a blue light-emitting diode. The emission spectrum of the light emitting device was measured and shown in FIG.
A blue light emitting diode with an emission wavelength centered at 450 nm was used. A large emission peak originating from the complex of Example 2 appears at 615 nm. In addition, small emission peaks also appear near 590 nm, 660 nm, and 700 nm. As shown in Table 1, the complex of Example 2 gave a high external quantum efficiency of about 44%.

As is clear from the emission spectrum of FIG. 10, the light-emitting device manufactured using the complex of Example 2 can compensate for the red component lacking in the conventional white light-emitting device. A light source using this light emitting device is a white light source with extremely high color rendering. This can be used as a useful light source in fields where color discrimination or color rendering is particularly required, such as surgery and product displays.

Since the rare earth metal complex of the present embodiment can have such light absorption properties and light emission properties, it is more useful as a more efficient wavelength conversion optical functional material by combining it with a light emitting diode or laser diode as its excitation light source. can be used.

Furthermore, the rare earth metal complex of the present embodiment and an optical functional material which is a transparent solid carrier containing the same, and a light emitting device obtained by combining the same with a light emitting diode, a laser diode and other light emitters are similarly useful.

［化学式（Ｉ）において、
Ａ ^１ は、ＯＨ基又はＳＨ基を示し、
Ａ ^２ は、水素、重水素、Ｃ１～Ｃ３０のアルキル基、Ｃ３～Ｃ３０のシクロアルキル基、Ｃ１～Ｃ３０のパーハロゲン化アルキル基及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基から選択され、Ｃ１～Ｃ３０のアルキル基、Ｃ３～Ｃ３０のシクロアルキル基、Ｃ１～Ｃ３０のパーハロゲン化アルキル基及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基は、下記群（Ｇ）：
芳香族基；
パーハロゲン化芳香族基；
少なくとも１種のヘテロ原子を環中に含むヘテロ芳香族基；
直鎖又は分枝を有するＣ１～Ｃ３０のアルキル基；
直鎖又は分枝を有するＣ１～Ｃ３０のパーハロゲン化アルキル基；
直鎖又は分枝を有するＣ３～Ｃ３０のアルケニル基；
直鎖又は分枝を有するＣ３～Ｃ３０のパーハロゲン化アルケニル基；
Ｃ３～Ｃ３０のシクロアルキル基；
Ｃ３～Ｃ３０のパーハロゲン化シクロアルキル基；
Ｃ３～Ｃ３０のシクロアルケニル基；
Ｃ３～Ｃ３０のパーハロゲン化シクロアルケニル基；及び
Ｃ３～Ｃ３０のアルキニル基、並びに
ハロゲノ基から選択される一又は複数の置換基を有することができ、
Ａ ^３ は、Ｃ２～Ｃ３０のアルキレン基から選択され、そのアルキレン基は、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができ、
Ａ ^１ とアゾメチン基が共に結合するベンゼン環について、Ａ ^１ とアゾメチン基が結合していない、ベンゼン環の隣接する２つの炭素原子は、－Ｃ _４ Ｈ _４ －で接続されてナフタレン環を形成することができ、
そのベンゼン環と形成され得るナフタレン環は、更に、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができる］
で示される、二組の水酸基又はチオール基とアゾメチン基を有する配位子；及び

化学式（ＩＩ）：

［化学式（ＩＩ）において、
Ａ ^１ 及びＡ ^２ は、化学式（Ｉ）のものと同じであり、
Ａ ^４ は、Ｃ１～Ｃ３０のアルキル基から選択され、そのアルキル基は、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができ、
Ａ ^１ とアゾメチン基が共に結合するベンゼン環について、化学式（Ｉ）のベンゼン環と同様にナフタレン環を形成してよく、
そのベンゼン環と形成され得るナフタレン環は、更に、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができる］
で示される、一組の水酸基又はチオール基とアゾメチン基を有する配位子からなる群から選択される、水酸基又はチオール基とアゾメチン基を共に有する配位子、並びに

化学式（ＩＩＩ）

［化学式（ＩＩＩ）において、
Ｘは、両方共同一であっても各々が異なってもよい、上記群（Ｇ）から選択される置換基を示し、
Ｚは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、シアノ基、メチル基、エチル基、フェニル基、水素原子又は重水素原子を示す］
で示されるβ－ジケトナト配位子
が、共に配位し、

過塩素酸イオン、硝酸イオン、カルボン酸イオン、及びハロゲン化物イオンから選択される少なくとも１種の陰イオンが更に配位してよい、
希土類金属を含む、希土類金属錯体。
２．
下記化学式（ＩＶ）、（Ｖ）、（ＶＩ）、及び（ＶＩＩ）から選択される少なくとも１種の化学構造を含む、希土類金属錯体。

化学式（ＩＶ）：

［化学式（ＩＶ）において、
Ｌｎは、希土類金属原子を示し、ｎ１は、２又は３を示し、

β－ジケトナト配位子について、Ｘは、両方共同一であっても各々が異なってもよい、下記群（Ｇ）：
芳香族基；
パーハロゲン化芳香族基；
少なくとも１種のヘテロ原子を環中に含むヘテロ芳香族基；
直鎖又は分枝を有するＣ１～Ｃ３０のアルキル基；
直鎖又は分枝を有するＣ１～Ｃ３０のパーハロゲン化アルキル基；
直鎖又は分枝を有するＣ３～Ｃ３０のアルケニル基；
直鎖又は分枝を有するＣ３～Ｃ３０のパーハロゲン化アルケニル基；
Ｃ３～Ｃ３０のシクロアルキル基；
Ｃ３～Ｃ３０のパーハロゲン化シクロアルキル基；
Ｃ３～Ｃ３０のシクロアルケニル基；
Ｃ３～Ｃ３０のパーハロゲン化シクロアルケニル基；及び
Ｃ３～Ｃ３０のアルキニル基、
から選択される置換基を示し
Ｚは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、シアノ基、メチル基、エチル基、フェニル基、水素原子又は重水素原子を示し、ｎ２は、１～３の整数を示し、

Ｙは、過塩素酸イオン、硝酸イオン、カルボン酸イオン、及びハロゲン化物イオンから選択される少なくとも１種であってよく、ｎ３は、０～２の整数を示し、

二組の水酸基又はチオール基とアゾメチン基を有する配位子について、
Ａ ^１ は、ＯＨ基又はＳＨ基を示し、
Ａ ^２ は、水素、重水素、Ｃ１～Ｃ３０のアルキル基、Ｃ３～Ｃ３０のシクロアルキル基、Ｃ１～Ｃ３０のパーハロゲン化アルキル基及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基から選択され、Ｃ１～Ｃ３０のアルキル基、Ｃ３～Ｃ３０のシクロアルキル基、Ｃ１～Ｃ３０のパーハロゲン化アルキル基及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基は、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができ、
Ａ ^３ は、Ｃ２～Ｃ３０のアルキレン基から選択され、そのアルキレン基は、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができ、
Ａ ^１ とアゾメチン基が共に結合するベンゼン環について、Ａ ^１ とアゾメチン基が結合していない、ベンゼン環の隣接する２つの炭素原子は、－Ｃ _４ Ｈ _４ －で接続されてナフタレン環を形成することができ、
そのベンゼン環と形成され得るナフタレン環は、更に、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができ、
ｎ４は、１～３の整数を示す］、

化学式（Ｖ）：

［化学式（Ｖ）において、
ｎ５は、２以上の整数を示すほかは、化学式（ＩＶ）のものと同様である］、

化学式（ＶＩ）：

［化学式（ＶＩ）において、
ｎ６は、１以上の整数を示すほかは、化学式（ＩＶ）のものと同様である］、

化学式（ＶＩＩ）：

［化学式（ＶＩＩ）において、
一組の水酸基又はチオール基とアゾメチン基を有する配位子について、
Ａ ^１ は、ＯＨ基又はＳＨ基を示し、
Ａ ^２ は、水素、重水素、Ｃ１～Ｃ３０のアルキル基、Ｃ３～Ｃ３０のシクロアルキル基、Ｃ１～Ｃ３０のパーハロゲン化アルキル基及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基から選択され、Ｃ１～Ｃ３０のアルキル基、Ｃ３～Ｃ３０のシクロアルキル基、Ｃ１～Ｃ３０のパーハロゲン化アルキル基及びＣ３～Ｃ３０のパーハロゲン化シクロアルキル基は、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができ、
Ａ ^４ は、Ｃ１～３０のアルキル基から選択され、そのアルキル基は、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができ、
Ａ ^１ とアゾメチン基が共に結合するベンゼン環について、化学式（ＩＶ）と同様にナフタレン環を形成してよく、
そのベンゼン環と形成され得るナフタレン環は、更に、上記群（Ｇ）並びにハロゲノ基から選択される一又は複数の置換基を有することができ、
ｎ４は、１～３の整数を示す
ほかは、化学式（ＩＶ）のものと同様である］。
３．
４５０ｎｍの入射光に関する反射率が、５０％以下であり、かつ５５０ｎｍの入射光に関する反射率が、６０％以上である、上記１又は２に記載の希土類金属錯体。
４．
３８０ｎｍ及び４５０ｎｍの光で励起した場合、外部量子効率が、５％以上である上記１～３のいずれか一つに記載の希土類金属錯体。
５．
上記１～４のいずれか一つに記載の希土類金属錯体を含む光機能材料用透明固体担体。
６．
上記１～４のいずれか一つに記載の希土類金属錯体を、透明なマトリックス中に分散させることを含む、上記５に記載の透明固体担体の製造方法。
７．
上記１～４のいずれか一つに記載の希土類金属錯体又は上記５に記載の透明固体担体と、発光ダイオード又はレーザーダイオードとを組み合わせた、発光装置。 Provided is a novel trivalent rare earth complex having both a ligand having a hydroxyl group or a thiol group and an azomethine group and a β-diketonato ligand.
The new trivalent rare earth complex can preferably be used as a wavelength conversion member, and more preferably can absorb and emit light in the ultraviolet to blue light region.
Further, the trivalent rare earth metal complex more preferably has a wider excitation wavelength range, a higher absorbance, a lower reflectance, and a higher external quantum efficiency. Also, the wavelength conversion efficiency is higher and the emission intensity is higher.
The rare earth metal complex preferably has excellent wavelength conversion efficiency and is useful as a wavelength conversion material and a light emitting device using it.

This specification includes the following embodiments.
1.
Chemical formula (I):

[In the chemical formula (I),
A ¹ represents an OH group or an SH group,
A ² is selected from hydrogen, deuterium, C1-C30 alkyl groups, C3-C30 cycloalkyl groups, C1-C30 perhalogenated alkyl groups and C3-C30 perhalogenated cycloalkyl groups; The C30 alkyl group, the C3-C30 cycloalkyl group, the C1-C30 perhalogenated alkyl group and the C3-C30 perhalogenated cycloalkyl group are selected from the following group (G):
aromatic group;
perhalogenated aromatic groups;
heteroaromatic groups containing at least one heteroatom in the ring;
C1-C30 alkyl group having a straight or branched chain;
a C1-C30 perhalogenated alkyl group having a straight or branched chain;
straight or branched C3-C30 alkenyl group;
straight or branched C3-C30 perhalogenated alkenyl group;
C3-C30 cycloalkyl group;
a C3-C30 perhalogenated cycloalkyl group;
C3-C30 cycloalkenyl group;
C3-C30 perhalogenated cycloalkenyl groups; and
a C3-C30 alkynyl group, and
can have one or more substituents selected from halogeno groups,
A ³ is selected from C2-C30 alkylene groups, which alkylene groups may have one or more substituents selected from the above group (G) and halogeno groups,
For the benzene ring to which A ¹ and the azomethine group are bonded together, two adjacent carbon atoms of the benzene ring to which A ¹ and the azomethine group are not bonded are connected by —C ₄ H ₄ — to form a naphthalene ring. It is possible,
The naphthalene ring that can be formed with the benzene ring can further have one or more substituents selected from the above group (G) and a halogeno group]
a ligand having two sets of hydroxyl or thiol groups and an azomethine group; and

Chemical formula (II):

[In the chemical formula (II),
A ¹ and A ² are the same as those of formula (I);
A ⁴ is selected from C1 to C30 alkyl groups, which alkyl groups may have one or more substituents selected from the above group (G) and halogeno groups;
Regarding the benzene ring to which A1 and the azomethine group are bonded together, a naphthalene ring may be formed in the same manner as the benzene ring of the chemical formula (I) ^,
The naphthalene ring that can be formed with the benzene ring can further have one or more substituents selected from the above group (G) and a halogeno group]
A ligand having both a hydroxyl group or a thiol group and an azomethine group, selected from the group consisting of ligands having a set of hydroxyl or thiol groups and an azomethine group, and

chemical formula (III)

[In the chemical formula (III),
X represents a substituent selected from the above group (G), both of which may be the same or each may be different;
Z represents a fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, methyl group, ethyl group, phenyl group, hydrogen atom or deuterium atom]
β-diketonato ligand represented by
coordinate together,

at least one anion selected from perchlorate ions, nitrate ions, carboxylate ions, and halide ions may be further coordinated;
A rare earth metal complex containing a rare earth metal.
2.
A rare earth metal complex comprising at least one chemical structure selected from the following chemical formulas (IV), (V), (VI), and (VII).

Chemical formula (IV):

[In the chemical formula (IV),
Ln represents a rare earth metal atom, n1 represents 2 or 3,

For β-diketonato ligands, X may both be the same or each be different, group (G) below:
aromatic group;
perhalogenated aromatic groups;
heteroaromatic groups containing at least one heteroatom in the ring;
C1-C30 alkyl group having a straight or branched chain;
a C1-C30 perhalogenated alkyl group having a straight or branched chain;
straight or branched C3-C30 alkenyl group;
straight or branched C3-C30 perhalogenated alkenyl group;
C3-C30 cycloalkyl group;
a C3-C30 perhalogenated cycloalkyl group;
C3-C30 cycloalkenyl group;
C3-C30 perhalogenated cycloalkenyl groups; and
a C3-C30 alkynyl group,
indicates a substituent selected from
Z represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a methyl group, an ethyl group, a phenyl group, a hydrogen atom or a deuterium atom, n2 represents an integer of 1 to 3,

Y may be at least one selected from perchlorate ions, nitrate ions, carboxylate ions, and halide ions, n3 is an integer of 0 to 2,

For ligands having two pairs of hydroxyl or thiol groups and an azomethine group,
A ¹ represents an OH group or an SH group,
A ² is selected from hydrogen, deuterium, C1-C30 alkyl groups, C3-C30 cycloalkyl groups, C1-C30 perhalogenated alkyl groups and C3-C30 perhalogenated cycloalkyl groups; The C30 alkyl group, the C3-C30 cycloalkyl group, the C1-C30 perhalogenated alkyl group and the C3-C30 perhalogenated cycloalkyl group are one or more selected from the above group (G) and a halogeno group can have a substituent of
A ³ is selected from C2-C30 alkylene groups, which alkylene groups may have one or more substituents selected from the above group (G) and halogeno groups,
For the benzene ring to which A ¹ and the azomethine group are bonded together, two adjacent carbon atoms of the benzene ring to which A ¹ and the azomethine group are not bonded are connected by —C ₄ H ₄ — to form a naphthalene ring. It is possible,
The naphthalene ring that can be formed with the benzene ring can further have one or more substituents selected from the above group (G) and a halogeno group,
n4 represents an integer of 1 to 3],

Chemical formula (V):

[In the chemical formula (V),
n5 is the same as that of chemical formula (IV) except that it represents an integer of 2 or more],

Chemical formula (VI):

[In the chemical formula (VI),
n6 is the same as that of chemical formula (IV) except that it represents an integer of 1 or more],

Chemical formula (VII):

[In the chemical formula (VII),
For a ligand having a pair of hydroxyl or thiol groups and an azomethine group,
A ¹ represents an OH group or an SH group,
A ² is selected from hydrogen, deuterium, C1-C30 alkyl groups, C3-C30 cycloalkyl groups, C1-C30 perhalogenated alkyl groups and C3-C30 perhalogenated cycloalkyl groups; The C30 alkyl group, the C3-C30 cycloalkyl group, the C1-C30 perhalogenated alkyl group and the C3-C30 perhalogenated cycloalkyl group are one or more selected from the above group (G) and a halogeno group can have a substituent of
A ⁴ is selected from C1-30 alkyl groups, which alkyl groups may have one or more substituents selected from the above group (G) and halogeno groups;
The benzene ring to which A1 and the azomethine group are bonded together may form a naphthalene ring in the same manner as in chemical formula (IV) ^,
The naphthalene ring that can be formed with the benzene ring can further have one or more substituents selected from the above group (G) and a halogeno group,
n4 represents an integer of 1 to 3
Others are the same as those of chemical formula (IV)].
3.
3. The rare earth metal complex according to 1 or 2 above, wherein the reflectance for incident light of 450 nm is 50% or less and the reflectance for incident light of 550 nm is 60% or more.
4.
4. The rare earth metal complex according to any one of 1 to 3 above, which has an external quantum efficiency of 5% or more when excited by light of 380 nm and 450 nm.
5.
A transparent solid carrier for an optical functional material, comprising the rare earth metal complex according to any one of 1 to 4 above.
6.
6. The method for producing the transparent solid carrier according to 5 above, which comprises dispersing the rare earth metal complex according to any one of 1 to 4 above in a transparent matrix.
7.
A light-emitting device comprising a combination of the rare earth metal complex according to any one of 1 to 4 above or the transparent solid support according to 5 above, and a light-emitting diode or laser diode.

Claims (7)

a rare earth metal complex or a transparent solid support for an optical functional material containing the rare earth metal complex;
A light-emitting device combined with a light-emitting diode or laser diode that emits light in the ultraviolet to blue region and excites the rare earth metal complex,
The rare earth metal complex is

Chemical formula (I):

[In the chemical formula (I),
A ¹ represents an OH group or an SH group,
A ² is selected from hydrogen, deuterium, C1-C30 alkyl groups, C3-C30 cycloalkyl groups, C1-C30 perhalogenated alkyl groups and C3-C30 perhalogenated cycloalkyl groups; The C30 alkyl group, the C3-C30 cycloalkyl group, the C1-C30 perhalogenated alkyl group and the C3-C30 perhalogenated cycloalkyl group are selected from the following group (G):
aromatic group;
perhalogenated aromatic groups;
heteroaromatic groups containing at least one heteroatom in the ring;
C1-C30 alkyl group having a straight or branched chain;
a C1-C30 perhalogenated alkyl group having a straight or branched chain;
straight or branched C3-C30 alkenyl group;
straight or branched C3-C30 perhalogenated alkenyl group;
C3-C30 cycloalkyl group;
a C3-C30 perhalogenated cycloalkyl group;
C3-C30 cycloalkenyl group;
C3-C30 perhalogenated cycloalkenyl groups; and C3-C30 alkynyl groups, and halogeno groups.
A ³ is selected from C2-C30 alkylene groups, which alkylene groups may have one or more substituents selected from the above group (G) and halogeno groups,
For the benzene ring to which A ¹ and the azomethine group are bonded together, two adjacent carbon atoms of the benzene ring to which A ¹ and the azomethine group are not bonded are connected by —C ₄ H ₄ — to form a naphthalene ring. It is possible,
The naphthalene ring that can be formed with the benzene ring can further have one or more substituents selected from the above group (G) and a halogeno group], a pair of hydroxyl or thiol groups and azomethine a ligand bearing a group; and

Chemical formula (II):

[In the chemical formula (II),
A ¹ and A ² are the same as those of formula (I);
A ⁴ is selected from C1 to C30 alkyl groups, which alkyl groups may have one or more substituents selected from the above group (G) and halogeno groups;
Regarding the benzene ring to which ^A1 and the azomethine group are bonded together, a naphthalene ring may be formed in the same manner as the benzene ring of the chemical formula (I),
The naphthalene ring that can be formed with the benzene ring can further have one or more substituents selected from the above group (G) and a halogeno group], a set of hydroxyl or thiol group and azomethine a ligand having one hydroxyl group or thiol group and an azomethine group , selected from the group consisting of ligands having groups;

chemical formula (III)

[In the chemical formula (III),
X represents a substituent selected from the above group (G), both of which may be the same or each may be different;
Z represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a methyl group, an ethyl group, a phenyl group, a hydrogen atom or a deuterium atom] is simultaneously coordinated a rare earth metal comprising
At least one anion selected from perchlorate ions, nitrate ions, carboxylate ions, and halide ions may be further coordinated, comprising the rare earth metal ,
The rare earth metal is Eu,
The light emitting device , wherein the rare earth metal complex has an external quantum efficiency of 5% or more when excited by light of 450 nm . a rare earth metal complex or a transparent solid support for an optical functional material containing the rare earth metal complex;
A light-emitting device combined with a light-emitting diode or laser diode that emits light in the ultraviolet to blue region and excites the rare earth metal complex,
The rare earth metal complex comprises at least one chemical structure selected from the following chemical formulas (IV), (V), (VI), and (VII),
The light emitting device , wherein the rare earth metal complex has an external quantum efficiency of 5% or more when excited by light of 450 nm .

Chemical formula (IV):

[In the chemical formula (IV),
Ln represents Eu , n1 represents 2 or 3,
For β-diketonato ligands, X may both be the same or each be different, group (G) below:
aromatic group;
perhalogenated aromatic groups;
heteroaromatic groups containing at least one heteroatom in the ring;
C1-C30 alkyl group having a straight or branched chain;
a C1-C30 perhalogenated alkyl group having a straight or branched chain;
straight or branched C3-C30 alkenyl group;
straight or branched C3-C30 perhalogenated alkenyl group;
C3-C30 cycloalkyl group;
a C3-C30 perhalogenated cycloalkyl group;
C3-C30 cycloalkenyl group;
a C3-C30 perhalogenated cycloalkenyl group; and a C3-C30 alkynyl group, wherein Z is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a methyl group, an ethyl group. , represents a phenyl group, a hydrogen atom or a deuterium atom, n2 represents an integer of 1 to 3,
Y may be at least one selected from perchlorate ions, nitrate ions, carboxylate ions, and halide ions, n3 is an integer of 0 to 2,
For ligands having two pairs of hydroxyl or thiol groups and an azomethine group,
A ¹ represents an OH group or an SH group,
A ² is selected from hydrogen, deuterium, C1-C30 alkyl groups, C3-C30 cycloalkyl groups, C1-C30 perhalogenated alkyl groups and C3-C30 perhalogenated cycloalkyl groups; The C30 alkyl group, the C3-C30 cycloalkyl group, the C1-C30 perhalogenated alkyl group and the C3-C30 perhalogenated cycloalkyl group are one or more selected from the above group (G) and a halogeno group can have a substituent of
A ³ is selected from C2-C30 alkylene groups, which alkylene groups may have one or more substituents selected from the above group (G) and halogeno groups,
For the benzene ring to which A ¹ and the azomethine group are bonded together, two adjacent carbon atoms of the benzene ring to which A ¹ and the azomethine group are not bonded are connected by —C ₄ H ₄ — to form a naphthalene ring. It is possible,
The naphthalene ring that can be formed with the benzene ring can further have one or more substituents selected from the above group (G) and a halogeno group,
n4 represents an integer of 1 to 3],

Chemical formula (V):

[In the chemical formula (V),
n5 is the same as that of chemical formula (IV) except that it represents an integer of 2 or more],

Chemical formula (VI):

[In the chemical formula (VI),
n6 is the same as that of chemical formula (IV) except that it represents an integer of 1 or more],

Chemical formula (VII):

[In the chemical formula (VII),
For a ligand having a pair of hydroxyl or thiol groups and an azomethine group,
A ¹ represents an OH group or an SH group,
A ² is selected from hydrogen, deuterium, C1-C30 alkyl groups, C3-C30 cycloalkyl groups, C1-C30 perhalogenated alkyl groups and C3-C30 perhalogenated cycloalkyl groups; The C30 alkyl group, the C3-C30 cycloalkyl group, the C1-C30 perhalogenated alkyl group and the C3-C30 perhalogenated cycloalkyl group are one or more selected from the above group (G) and a halogeno group can have a substituent of
A ⁴ is selected from C1-30 alkyl groups, which alkyl groups may have one or more substituents selected from the above group (G) and halogeno groups;
The benzene ring to which ^A1 and the azomethine group are bonded together may form a naphthalene ring in the same manner as in chemical formula (IV),
The naphthalene ring that can be formed with the benzene ring can further have one or more substituents selected from the above group (G) and a halogeno group,
n4 is the same as that of chemical formula (IV), except that n4 represents an integer of 1 to 3]. 3. The light-emitting device according to claim 1, wherein the rare earth metal complex has a reflectance of 50% or less for incident light of 450 nm and a reflectance of 60% or more for incident light of 550 nm. The light emitting device according to any one of claims 1 to 3, wherein the rare earth metal complex has an external quantum efficiency of 5% or more when excited by light of 380 nm. 5. The light-emitting device according to claim 1, wherein said light-emitting diode or laser diode is a nitride semiconductor light-emitting element including a nitride semiconductor layer containing In as a light-emitting layer. The light-emitting device according to any one of claims 1 to 5 , wherein the transparent solid carrier for an optical functional material is a cured product obtained by dispersing the rare earth metal complex in a silicone resin. The light-emitting device according to any one of claims 1 to 6 , wherein the light-emitting device emits white light.

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