JP7023551B1 - Complex compounds, inks and resin compositions - Google Patents

Complex compounds, inks and resin compositions Download PDF

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JP7023551B1
JP7023551B1 JP2021068103A JP2021068103A JP7023551B1 JP 7023551 B1 JP7023551 B1 JP 7023551B1 JP 2021068103 A JP2021068103 A JP 2021068103A JP 2021068103 A JP2021068103 A JP 2021068103A JP 7023551 B1 JP7023551 B1 JP 7023551B1
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昌信 槌本
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

【課題】発光強度が高い錯体化合物と、これを含むインク及び樹脂組成物の提供。【解決手段】下記一般式(1)で表される、錯体化合物。X+[Eu(L1)(L2)]-・・・(1)式(1)中、L1及びL2は各々独立に、下記一般式(2)で表される化合物から誘導される、Eu錯体の配位子であり、X+は対カチオンである。[化1]TIFF0007023551000028.tif44170式(2)中、R1及びR2は各々独立に、水素原子、メチル基、フェニル基である。【選択図】なしPROBLEM TO BE SOLVED: To provide a complex compound having high emission intensity, and an ink and a resin composition containing the complex compound. SOLUTION: A complex compound represented by the following general formula (1). X + [Eu (L1) (L2)]-... In the formula (1) of (1), L1 and L2 are independently derived from the compound represented by the following general formula (2) of the Eu complex. It is a ligand and X + is a counter cation. [Chemical formula 1] In TIFF0007023551000028.tif44170 formula (2), R1 and R2 are independently hydrogen atoms, methyl groups, and phenyl groups, respectively. [Selection diagram] None

Description

本発明は、錯体化合物、インク及び樹脂組成物に関する。 The present invention relates to complex compounds, inks and resin compositions.

ユウロピウム(III)イオンを含む化合物には、紫外線を照射すると強い赤色発光を示すものがあり、インビジブルインク、発光標識試薬、有機EL素子、太陽電池の波長変換材料、白色LED等の発光材料として使用されている。
ユウロピウムを用いた高い発光強度を示す発光材料として、例えばClを置換基として有するsalen型シッフ塩基であるN,N’-ビス-3,5-ジクロロサリチリデンエチレンジアミン(H(3,5-Clsalen))を配位子とするユウロピウム(III)単核錯体が提案されている(例えば非特許文献1、2)。
Some compounds containing europium (III) ions emit strong red light when irradiated with ultraviolet rays, and are used as light emitting materials for invisible inks, light emitting labeling reagents, organic EL devices, wavelength conversion materials for solar cells, white LEDs, etc. Has been done.
As a light emitting material using europium that exhibits high light emission intensity, for example, N, N'-bis-3,5-dichlorosalicylideneethylenediamine (H 2 (3,5-), which is a salen-type Schiff base having Cl as a substituent, is used. A europium (III) mononuclear complex having Clsalen)) as a ligand has been proposed (for example, Non-Patent Documents 1 and 2).

S. Ebato, et. al., Chemistry Letters, Vol.39, No.7, 2010, p.706-707.S. Ebato, et. Al., Chemistry Letters, Vol.39, No.7, 2010, p.706-707. M. Tsuchimoto, et. al., Polyhedron, Vol.148, 2018, p.118-123.M. Tsuchimoto, et. Al., Polyhedron, Vol.148, 2018, p.118-123.

しかし、非特許文献1、2に記載の単核錯体には未だ改善の余地があり、さらなる発光強度の向上が求められる。
本発明は、発光強度が高い錯体化合物と、これを含むインク及び樹脂組成物を提供することを目的とする。
However, the mononuclear complexes described in Non-Patent Documents 1 and 2 still have room for improvement, and further improvement in emission intensity is required.
An object of the present invention is to provide a complex compound having high emission intensity, and an ink and a resin composition containing the complex compound.

本発明は、下記の態様を有する。
[1] 下記一般式(1)で表される、錯体化合物。
[Eu(L)(L)] ・・・(1)
式(1)中、L及びLは各々独立に、下記一般式(2)で表される化合物から誘導される、Eu錯体の配位子であり、Xは対カチオンである。
The present invention has the following aspects.
[1] A complex compound represented by the following general formula (1).
X + [Eu (L 1 ) (L 2 ) ] -... (1)
In the formula (1), L 1 and L 2 are each independently derived from the compound represented by the following general formula (2), and are the ligands of the Eu complex, and X + is a counter cation.

Figure 0007023551000001
Figure 0007023551000001

式(2)中、R及びRは各々独立に、水素原子、メチル基、フェニル基である。 In formula (2), R 1 and R 2 are independently hydrogen atoms, methyl groups, and phenyl groups, respectively.

[2] 前記[1]の錯体化合物を含む、インク。
[3] 前記[1]の錯体化合物を含む、樹脂組成物。
[2] An ink containing the complex compound of the above [1].
[3] A resin composition containing the complex compound of the above [1].

本発明によれば、発光強度が高い錯体化合物と、これを含むインク及び樹脂組成物を提供できる。 According to the present invention, it is possible to provide a complex compound having high emission intensity, and an ink and a resin composition containing the complex compound.

実施例2で得られた錯体化合物の分子構造図である。It is a molecular structure diagram of the complex compound obtained in Example 2. FIG. 実施例6で得られた錯体化合物の分子構造図である。It is a molecular structure diagram of the complex compound obtained in Example 6. 実施例6及び比較例1で得られた錯体化合物のアセトニトリル溶液の吸収スペクトルである。6 is an absorption spectrum of an acetonitrile solution of the complex compound obtained in Example 6 and Comparative Example 1. 実施例2、4、6で得られた錯体化合物のアセトニトリル溶液の吸収スペクトルである。6 is an absorption spectrum of an acetonitrile solution of the complex compound obtained in Examples 2, 4 and 6. 実施例6で得られた錯体化合物のアセトニトリル溶液の発光スペクトルである。It is an emission spectrum of the acetonitrile solution of the complex compound obtained in Example 6. 実施例6で得られた錯体化合物の固体の発光スペクトルである。6 is an emission spectrum of a solid of the complex compound obtained in Example 6. 実施例6で得られた錯体化合物を含むフィルムの発光スペクトルである。6 is an emission spectrum of a film containing the complex compound obtained in Example 6. 実施例2、7及び比較例1、2で得られた錯体化合物を含むフィルムの発光スペクトルである。It is an emission spectrum of the film containing the complex compound obtained in Examples 2 and 7 and Comparative Examples 1 and 2. 実施例4、8及び比較例1で得られた錯体化合物を含むフィルムの発光スペクトルである。It is an emission spectrum of the film containing the complex compound obtained in Examples 4 and 8 and Comparative Example 1.

以下、本発明を詳細に説明する。
ただし、以下に説明する実施の形態は、発明の趣旨をより良く理解させるため具体的に説明するものであり、特に指定のない限り発明内容を限定するものではなく、本発明の趣旨を逸脱しない範囲で種々の変更が可能である。
Hereinafter, the present invention will be described in detail.
However, the embodiments described below are specifically described in order to better understand the gist of the invention, and do not limit the content of the invention unless otherwise specified, and do not deviate from the gist of the present invention. Various changes are possible within the range.

[錯体化合物]
本発明の錯体化合物は、下記一般式(1)で表されるユウロピウム(III)単核錯体である。
[Eu(L)(L)] ・・・(1)
式(1)中、L及びLは各々独立に、下記一般式(2)で表される化合物から誘導される、Eu錯体の配位子であり、Xは対カチオンである。
対カチオンとしては、例えば(C2n+1、(C2m+1NH、PPh 、アルカリ金属イオン(例えばNa、K等)、アルカリ金属の錯イオン(例えばクラウンエーテル錯体等)、銀イオン(Ag)、銀の錯イオン(例えば[Ag(PPh等)などが挙げられる。なお、nは1~5の整数であり、mは1~5の整数であり、Phはフェニル基である。
[Complex compound]
The complex compound of the present invention is a europium (III) mononuclear complex represented by the following general formula (1).
X + [Eu (L 1 ) (L 2 ) ] -... (1)
In the formula (1), L 1 and L 2 are each independently derived from the compound represented by the following general formula (2), and are the ligands of the Eu complex, and X + is a counter cation.
Examples of the counter cation include (C n H 2n + 1 ) 4 N + , (C m H 2m + 1 ) 3 NH + , PPh 4 + , alkali metal ions (for example, Na + , K + , etc.), and alkali metal complex ions (for example). Crown ether complexes, etc.), silver ions (Ag + ), silver complex ions (eg, [Ag (PPh 3 ) 4 ] + , etc.) and the like. Note that n is an integer of 1 to 5, m is an integer of 1 to 5, and Ph is a phenyl group.

Figure 0007023551000002
Figure 0007023551000002

式(2)中、R及びRは各々独立に、水素原子、メチル基、フェニル基である。
及びRとしては各々独立に、発光強度がより高まる観点から水素原子、フェニル基が好ましく、R及びRの両方が水素原子であるか、フェニル基であることが好ましい。
式(2)中のトリフルオロメチル基(CF)の位置は、3位でもよいし、4位でもよいし、5位でもよいが、錯体化合物の安定性及び透明性が高まり、インビジブルインクの材料として好適に用いられる観点から、3位又は5位が好ましい。すなわち、前記一般式(2)で表される化合物としては、下記一般式(21)で表される化合物又は下記一般式(22)で表される化合物が好ましい。
In formula (2), R 1 and R 2 are independently hydrogen atoms, methyl groups, and phenyl groups, respectively.
As R 1 and R 2 , hydrogen atoms and phenyl groups are preferable from the viewpoint of further increasing the emission intensity, and it is preferable that both R 1 and R 2 are hydrogen atoms or phenyl groups.
The position of the trifluoromethyl group (CF 3 ) in the formula (2) may be the 3-position, the 4-position, or the 5-position, but the stability and transparency of the complex compound are enhanced, and the invisible ink is used. From the viewpoint of being preferably used as a material, the 3-position or 5-position is preferable. That is, as the compound represented by the general formula (2), the compound represented by the following general formula (21) or the compound represented by the following general formula (22) is preferable.

Figure 0007023551000003
Figure 0007023551000003

式(21)及び式(22)中、R及びRは各々独立に、水素原子、メチル基、フェニル基である。 In formulas (21) and (22), R 1 and R 2 are independently hydrogen atoms, methyl groups, and phenyl groups, respectively.

なお、本発明において、前記一般式(2)で表される化合物を「化合物(2)」又は「トリフルオロメチル基を有するsalen型シッフ塩基」ともいう。特に、式(2)中のR及びRが水素原子である場合において、トリフルオロメチル基を3位の位置に有する化合物を「H(3-CFsalen)」と略し、トリフルオロメチル基を4位の位置に有する化合物を「H(4-CFsalen)」と略し、トリフルオロメチル基を5位の位置に有する化合物を「H(5-CFsalen)」と略す。また、R及びRがフェニル基である場合において、トリフルオロメチル基を3位の位置に有する化合物を「H(3-CFsal-(R,R)-stien)」又は「H(3-CFsal-(S,S)-stien)」と略し、トリフルオロメチル基を4位の位置に有する化合物を「H(4-CFsal-(R,R)-stien)」又は「H(4-CFsal-(S,S)-stien)」と略し、トリフルオロメチル基を5位の位置に有する化合物を「H(5-CFsal-(R,R)-stien)」又は「H(5-CFsal-(S,S)-stien)」と略す。
また、本発明において、前記一般式(21)で表される化合物を「化合物(21)」ともいい、前記一般式(22)で表される化合物を「化合物(22)」ともいう。化合物(21)は、トリフルオロメチル基を3位の位置に有する化合物であり、化合物(22)は、トリフルオロメチル基を5位の位置に有する化合物である。
In the present invention, the compound represented by the general formula (2) is also referred to as "compound (2)" or "salen-type Schiff base having a trifluoromethyl group". In particular, when R 1 and R 2 in the formula (2) are hydrogen atoms, the compound having a trifluoromethyl group at the 3-position position is abbreviated as "H 2 (3-CF 3 salon)" and is trifluoro. The compound having a methyl group at the 4-position position is abbreviated as "H 2 (4-CF 3 salon)", and the compound having a trifluoromethyl group at the 5-position position is referred to as "H 2 (5-CF 3 salon)". Abbreviate. Further, when R 1 and R 2 are phenyl groups, the compound having a trifluoromethyl group at the 3-position position is "H 2 (3-CF 3 sal- (R, R) -sien)" or "H". 2 (3-CF 3 sal- (S, S) -steen) ”is abbreviated as“ H 2 (4-CF 3 sal- (R, R) -steen), which is a compound having a trifluoromethyl group at the 4-position position. ) ”Or“ H 2 (4-CF 3 sal- (S, S) -steen) ”, and the compound having a trifluoromethyl group at the 5-position position is“ H 2 (5-CF 3 sal- (R). , R) -steen) "or" H 2 (5-CF 3 sal- (S, S) -steen) ".
Further, in the present invention, the compound represented by the general formula (21) is also referred to as "compound (21)", and the compound represented by the general formula (22) is also referred to as "compound (22)". Compound (21) is a compound having a trifluoromethyl group at the 3-position position, and compound (22) is a compound having a trifluoromethyl group at the 5-position position.

化合物(2)は、式(2)中のOとNがEuに結合することで、下記一般式(1A)で表されるように、Euに配位する。すなわち、本発明の錯体化合物は、下記一般式(1A)で表される。 The compound (2) is coordinated to Eu as represented by the following general formula (1A) by binding O and N in the formula (2) to Eu. That is, the complex compound of the present invention is represented by the following general formula (1A).

Figure 0007023551000004
Figure 0007023551000004

式(1)中のLは、式(1A)中のO11-A11-N11-A12-N12-A13-O12(ただし、O11とO12とN11とN12のEuと結合する結合手は省略する。)に相当し、式(1)中のLは、式(1A)中のO21-A21-N21-A22-N22-A23-O22(ただし、O21とO22とN21とN22のEuと結合する結合手は省略する。)に相当する。
式(1A)中のO11-A11-N11-A12-N12-A13-O12は下記一般式(2A)であり、式(1A)中のO21-A21-N21-A22-N22-A23-O22は下記一般式(2B)であり、式(1A)中のXは対カチオンである。なお、下記一般式(2A)において、O11とO12とN11とN12のEuと結合する結合手は省略する。また、下記一般式(2B)において、O21とO22とN21とN22のEuと結合する結合手は省略する。
L 1 in the formula (1) is O 11 -A 11 -N 11 -A 12 -N 12 -A 13 -O 12 in the formula (1A) (however, O 11 and O 12 and N 11 and N 12 ). The binding hand that binds to Eu is omitted.), And L 2 in the formula (1) is O 21 -A 21 -N 21 -A 22 -N 22 -A 23- in the formula (1A). It corresponds to O 22 (however, the coupling hand that binds to Eu of O 21 and O 22 and N 21 and N 22 is omitted).
O 11 -A 11 -N 11 -A 12 -N 12 -A 13 -O 12 in the formula (1A) is the following general formula (2A), and O 21 -A 21 -N 21 in the formula (1A). -A 22 -N 22 -A 23 -O 22 is the following general formula (2B), and X + in the formula (1A) is a counter cation. In the following general formula (2A), the bond that binds Eu of O 11 and O 12 and N 11 and N 12 is omitted. Further, in the following general formula (2B), the bond that binds Eu of O 21 and O 22 and N 21 and N 22 is omitted.

Figure 0007023551000005
Figure 0007023551000005

式(2)及び式(2)中、R及びRは各々独立に、水素原子、メチル基、フェニル基である。 In formula (2 A ) and formula (2 B ), R 1 and R 2 are independently hydrogen atoms, methyl groups, and phenyl groups, respectively.

前記一般式(1)で表される錯体化合物は、例えば以下のようにして製造できる。すなわち、本実施形態の錯体化合物の製造方法は、以下に示す工程(a)及び工程(b)を含む。
まず、溶媒中にて化合物(3)と化合物(4)とを反応させ、化合物(2)を得る(工程(a))。
The complex compound represented by the general formula (1) can be produced, for example, as follows. That is, the method for producing the complex compound of the present embodiment includes the following steps (a) and (b).
First, the compound (3) and the compound (4) are reacted in a solvent to obtain the compound (2) (step (a)).

Figure 0007023551000006
Figure 0007023551000006

化合物(3)としては、2-ヒドロキシ-3-トリフルオロメチルベンズアルデヒド、2-ヒドロキシ-4-トリフルオロメチルベンズアルデヒド、2-ヒドロキシ-5-トリフルオロメチルベンズアルデヒドが挙げられる。
化合物(4)としては、エチレンジアミン、(1R,2R)-1,2-ジフェニルエチレンジアミン、(1S,2S)-1,2-ジフェニルエチレンジアミン、(2R,3R)-2,3-ブタンジアミン、(2S,3S)-2,3-ブタンジアミンなどが挙げられる。
溶媒としては、メタノール、エタノール、プロパノール等のアルコール系溶媒などが挙げられる。
Examples of the compound (3) include 2-hydroxy-3-trifluoromethylbenzaldehyde, 2-hydroxy-4-trifluoromethylbenzaldehyde, and 2-hydroxy-5-trifluoromethylbenzaldehyde.
Examples of the compound (4) include ethylenediamine, (1R, 2R) -1,2-diphenylethylenediamine, (1S, 2S) -1,2-diphenylethylenediamine, (2R, 3R) -2,3-butanediamine, (2S). , 3S) -2,3-butanediamine and the like.
Examples of the solvent include alcoholic solvents such as methanol, ethanol and propanol.

化合物(3)と化合物(4)との反応割合、すなわち化合物(3)/化合物(4)で表されるモル比は、1.95~3が好ましく、2~2.5がより好ましい。モル比が上記範囲内であれば、未反応の化合物(3)や化合物(4)の割合が少なく、化合物(2)を高収率で得ることができる。
工程(a)の反応温度は、20~50℃が好ましく、25~45℃がより好ましい。
工程(a)の反応時間は、0.5~3時間が好ましく、1~2時間がより好ましい。
The reaction ratio between the compound (3) and the compound (4), that is, the molar ratio represented by the compound (3) / the compound (4) is preferably 1.95 to 3, more preferably 2 to 2.5. When the molar ratio is within the above range, the ratio of the unreacted compound (3) and the compound (4) is small, and the compound (2) can be obtained in a high yield.
The reaction temperature in the step (a) is preferably 20 to 50 ° C, more preferably 25 to 45 ° C.
The reaction time of the step (a) is preferably 0.5 to 3 hours, more preferably 1 to 2 hours.

次いで、溶媒中にて化合物(2)と化合物(5)と化合物(6)とを反応させ、前記一般式(1)で表される錯体化合物(以下、「化合物(1)」ともいう。)を得る(工程(b))。 Next, the compound (2), the compound (5), and the compound (6) are reacted in a solvent, and the complex compound represented by the general formula (1) (hereinafter, also referred to as “compound (1)”). (Step (b)).

Figure 0007023551000007
Figure 0007023551000007

化合物(5)は、ユウロピウム(III)を含む化合物である。化合物(5)としては、例えば酢酸ユウロピウム(III)n水和物、ユウロピウム(III)アセチルアセトナート二水和物などが挙げられる。
化合物(6)は、式(1)中のX(対カチオン)の由来となる化合物である。化合物(6)としては、例えばテトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド等のテトラアルキルアンモニウムヒドロキシド;テトラメチルアンモニウムブロミド、テトラエチルアンモニウムブロミド、テトラプロピルアンモニウムブロミド、テトラブチルアンモニウムブロミド、テトラペンチルアンモニウムブロミド等のテトラアルキルアンモニウムブロミド;テトラメチルアンモニウムクロリド、テトラエチルアンモニウムクロリド、テトラプロピルアンモニウムクロリド、テトラブチルアンモニウムクロリド、テトラペンチルアンモニウムクロリド等のテトラアルキルアンモニウムクロリド;テトラフェニルホスホニウムブロミド;テトラフェニルホスホニウムクロリド;テトラエチルホスホニウムブロミド;テトラブチルホスホニウムクロリド;トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン等のトリアルキルアミン;水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム等の水酸化アルカリ金属などが挙げられる。
なお、化合物(6)としてテトラアルキルアンモニウムブロミド、テトラアルキルアンモニウムクロリド、テトラフェニルホスホニウムブロミド、テトラフェニルホスホニウムクロリド、テトラエチルホスホニウムブロミド、テトラブチルホスホニウムクロリドなどを用いる場合には、化合物(2)のフェノール性水酸基のプロトンを引き抜くために、化合物(2)に対してモル比が1~3倍程度のピリジンやトリエチルアミンなどの塩基を加える。
溶媒としては、メタノール、エタノール、プロパノール等のアルコール系溶媒;アセトニトリル等のニトリル系溶媒などが挙げられる。
Compound (5) is a compound containing europium (III). Examples of the compound (5) include europium acetate (III) n hydrate, europium (III) acetylacetonate dihydrate and the like.
Compound (6) is a compound from which X + (anti-cation) in the formula (1) is derived. Examples of the compound (6) include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; tetramethylammonium bromide, tetraethylammonium bromide, and tetrapropylammonium. Tetraalkylammonium bromide such as bromide, tetrabutylammonium bromide, tetrapentylammonium bromide; tetraalkylammonium chloride such as tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrapentylammonium chloride; tetraphenyl. Phosphonium bromide; Tetraphenylphosphonium chloride; Tetraethylphosphonium bromide; Tetrabutylphosphonium chloride; Trialkylamines such as trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine; lithium hydroxide, sodium hydroxide, potassium hydroxide, water Examples thereof include alkali metal hydroxides such as rubidium oxide and cesium hydroxide.
When tetraalkylammonium bromide, tetraalkylammonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, tetraethylphosphonium bromide, tetrabutylphosphonium chloride and the like are used as the compound (6), the phenolic hydroxyl group of the compound (2). In order to extract the protons of compound (2), a base such as pyridine or triethylamine having a molar ratio of about 1 to 3 times that of compound (2) is added.
Examples of the solvent include alcohol solvents such as methanol, ethanol and propanol; and nitrile solvents such as acetonitrile.

化合物(2)と化合物(5)との反応割合、すなわち化合物(2)/化合物(5)で表されるモル比は、1.95~3が好ましく、2~2.2がより好ましい。モル比が上記範囲内であれば、未反応の化合物(2)や化合物(5)の割合が少なく、化合物(1)を高収率で得ることができる。
化合物(2)と化合物(6)との反応割合、すなわち化合物(2)/化合物(6)で表されるモル比は、0.5~2.0が好ましく、1.0~2.0がより好ましい。モル比が上記範囲内であれば、未反応の化合物(2)や化合物(6)の割合が少なく、化合物(1)を高収率で得ることができる。
工程(b)では、予め化合物(2)と化合物(5)と溶媒に溶解、もしくは懸濁させて混合溶液を調製しておき、得られた混合溶液と化合物(6)とを混合することが好ましい。
工程(b)の反応温度は、20~50℃が好ましく、25~45℃がより好ましい。
工程(b)の反応時間は、0.5~3時間が好ましく、1~2時間がより好ましい。
The reaction ratio between the compound (2) and the compound (5), that is, the molar ratio represented by the compound (2) / the compound (5) is preferably 1.95 to 3, more preferably 2 to 2.2. When the molar ratio is within the above range, the ratio of the unreacted compound (2) and the compound (5) is small, and the compound (1) can be obtained in a high yield.
The reaction ratio between the compound (2) and the compound (6), that is, the molar ratio represented by the compound (2) / the compound (6) is preferably 0.5 to 2.0, preferably 1.0 to 2.0. More preferred. When the molar ratio is within the above range, the ratio of the unreacted compound (2) and the compound (6) is small, and the compound (1) can be obtained in a high yield.
In the step (b), a mixed solution may be prepared by dissolving or suspending the compound (2) and the compound (5) in a solvent in advance, and the obtained mixed solution and the compound (6) may be mixed. preferable.
The reaction temperature in the step (b) is preferably 20 to 50 ° C, more preferably 25 to 45 ° C.
The reaction time of the step (b) is preferably 0.5 to 3 hours, more preferably 1 to 2 hours.

以上説明した本発明の錯体化合物は、ユウロピウム(III)に、上述した特定の配位子、すなわちトリフルオロメチル基を有するsalen型シッフ塩基が配位しているため、発光強度が高い。具体的には、固体の状態及び液体の状態で、320~380nmの波長の光を照射すると強く発光する。
特に、トリフルオロメチル基の位置が3位又は5位である錯体化合物は、白色光の下では、固体の状態で白色であり、液体の状態で無色透明である(すなわち、色として認識できない)ことから、インビジブルインクの材料として好適に用いられる。
なお、トリフルオロメチル基の位置が4位である錯体化合物は、白色光の下では、固体の状態及び液体の状態で共に薄い黄色である。
The complex compound of the present invention described above has high emission intensity because the above-mentioned specific ligand, that is, a salen-type Schiff base having a trifluoromethyl group is coordinated with europium (III). Specifically, it emits strong light when irradiated with light having a wavelength of 320 to 380 nm in a solid state and a liquid state.
In particular, the complex compound in which the position of the trifluoromethyl group is at the 3-position or 5-position is white in the solid state and colorless and transparent in the liquid state (that is, it cannot be recognized as a color) under white light. Therefore, it is suitably used as a material for invisible ink.
The complex compound in which the position of the trifluoromethyl group is at the 4-position is pale yellow in both the solid state and the liquid state under white light.

本発明の錯体化合物は、インビジブルインク、発光標識試薬、有機EL素子、太陽電池の波長変換材料、白色LED等の発光材料として好適である。 The complex compound of the present invention is suitable as a light emitting material such as an invisible ink, a light emitting labeling reagent, an organic EL element, a wavelength conversion material for a solar cell, and a white LED.

[インク]
本発明のインクは、上述した本発明の錯体化合物と、溶媒とを含み、必要に応じてバインダ、任意成分を含んでいてもよい。
溶媒としては、例えばアセトニトリル等のニトリル系溶媒;アセトン、メチルエチルケトン等のケトン系溶媒;エチルアセテート、プロピルアセテート等のエステル系溶媒;ジクロロメタン、クロロホルム等のハロゲン化アルキル系溶媒などが挙げられる。
[ink]
The ink of the present invention contains the above-mentioned complex compound of the present invention and a solvent, and may contain a binder and an optional component, if necessary.
Examples of the solvent include a nitrile solvent such as acetonitrile; a ketone solvent such as acetone and methyl ethyl ketone; an ester solvent such as ethyl acetate and propyl acetate; and an alkyl halide solvent such as dichloromethane and chloroform.

バインダとしては、例えばポリアクリレート又はポリメタクリレート(例えばポリメチルメタクリレート)、ポリスチレン、ポリオレフィン(例えばポリエチレン)、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリアリールスルホン、ポリアリールエーテル、ポリビニル誘導体、セルロース誘導体、ポリウレタン、ポリアミド、ポリイミド、ポリエステル、シリコーン樹脂などが挙げられる。 As the binder, for example, polyacrylate or polymethacrylate (for example, polymethylmethacrylate), polystyrene, polyolefin (for example, polyethylene), polycarbonate, polysulfone, polyethersulfone, polyarylsulfone, polyarylether, polyvinyl derivative, cellulose derivative, polyurethane, polyamide. , Polyethylene, polyester, silicone resin and the like.

任意成分としては、例えば界面活性剤、保湿剤、pH調整剤、消泡剤、酸化防止剤、還元防止剤などが挙げられる。 Examples of the optional component include a surfactant, a moisturizer, a pH adjuster, an antifoaming agent, an antioxidant, an antioxidant and the like.

錯体化合物の含有量は、インクの総質量に対して0.1~2質量%が好ましく、0.5~1質量%がより好ましい。
溶媒の含有量は、インクの総質量に対して98~99.9質量%が好ましく、99~99.5質量%がより好ましい。
バインダの含有量は、インクの総質量に対して5質量%以下が好ましく、1質量%以下がより好ましい。
任意成分の含有量は、インクの総質量に対して5質量%以下が好ましく、1質量%以下がより好ましい。
なお、インクに含まれる全ての成分の含有量の合計が、100質量%となるものとする。
The content of the complex compound is preferably 0.1 to 2% by mass, more preferably 0.5 to 1% by mass, based on the total mass of the ink.
The content of the solvent is preferably 98 to 99.9% by mass, more preferably 99 to 99.5% by mass, based on the total mass of the ink.
The binder content is preferably 5% by mass or less, more preferably 1% by mass or less, based on the total mass of the ink.
The content of the optional component is preferably 5% by mass or less, more preferably 1% by mass or less, based on the total mass of the ink.
It is assumed that the total content of all the components contained in the ink is 100% by mass.

本発明のインクは、上述した本発明の錯体化合物を含むので、白色光の下では無色透明又は薄い黄色であるが、320~380nmの波長の光を照射すると強く発光する。
よって、本発明のインクは、インビジブルインクとして好適である。
Since the ink of the present invention contains the complex compound of the present invention described above, it is colorless and transparent or pale yellow under white light, but emits strong light when irradiated with light having a wavelength of 320 to 380 nm.
Therefore, the ink of the present invention is suitable as an invisible ink.

[樹脂組成物]
本発明の樹脂組成物は、上述した本発明の錯体化合物と、樹脂成分とを含み、必要に応じて任意成分を含んでいてもよい。
樹脂成分としては、ポリアミド、ポリエステル、ポリカーボネート、ポリエーテルスルホン、ポリフェニレンエーテル、ポリフェニレンスルフィド、ポリエーテルエーテルケトン、ポリエーテルケトン、ポリイミド、ポリテトラフルオロエチレン、ポリエーテル、ポリオレフィン、液晶ポリマー、ポリアリレート、ポリスルホン、ポリアクリロニトリルスチレン、ポリスチレン、ポリアクリロニトリル、ポリメチルメタクリレート(PMMA)、ポリグリシジルメタクリレート(PGMA)、アクリロニトリル-ブタジエン-スチレンコポリマー(ABS)等の熱可塑性樹脂;エポキシ樹脂、ビニルエステル樹脂、不飽和ポリエステル樹脂、ポリイミド樹脂、マレイミド樹脂、フェノール樹脂等の熱硬化性樹脂などが挙げられる。
[Resin composition]
The resin composition of the present invention contains the above-mentioned complex compound of the present invention and a resin component, and may contain an arbitrary component if necessary.
Resin components include polyamide, polyester, polycarbonate, polyether sulfone, polyphenylene ether, polyphenylene sulfide, polyether ether ketone, polyether ketone, polyimide, polytetrafluoroethylene, polyether, polyolefin, liquid crystal polymer, polyarylate, polysulfone, etc. Thermoplastic resins such as polyacrylonitrile styrene, polystyrene, polyacrylonitrile, polymethylmethacrylate (PMMA), polyglycidylmethacrylate (PGMA), acrylonitrile-butadiene-styrene copolymer (ABS); epoxy resin, vinyl ester resin, unsaturated polyester resin, Examples thereof include thermocurable resins such as polyimide resin, maleimide resin, and phenol resin.

任意成分としては、例えば難燃剤、滑剤、離型剤、安定化剤、強化剤、酸化防止剤、可塑剤、粘度調整剤、顔料などが挙げられる。 Examples of the optional component include flame retardants, lubricants, mold release agents, stabilizers, strengthening agents, antioxidants, plasticizers, viscosity modifiers, pigments and the like.

錯体化合物の含有量は、樹脂組成物の総質量に対して0.1~1質量%が好ましく、0.2~0.5質量%がより好ましい。
樹脂成分の含有量は、樹脂組成物の総質量に対して99~99.9質量%が好ましく、99.5~99.8質量%が好ましい。
任意成分の含有量は、樹脂組成物の総質量に対して5質量%以下が好ましく、1質量%以下がより好ましい。
なお、樹脂組成物に含まれる全ての成分の含有量の合計が、100質量%となるものとする。
The content of the complex compound is preferably 0.1 to 1% by mass, more preferably 0.2 to 0.5% by mass, based on the total mass of the resin composition.
The content of the resin component is preferably 99 to 99.9% by mass, preferably 99.5 to 99.8% by mass, based on the total mass of the resin composition.
The content of the optional component is preferably 5% by mass or less, more preferably 1% by mass or less, based on the total mass of the resin composition.
It is assumed that the total content of all the components contained in the resin composition is 100% by mass.

本発明の樹脂組成物を成形することで成形体が得られる。
成形方法としては、例えば射出成形法、押出成形法、圧縮成形、ブロー成形法、カレンダー成形法などが挙げられる。
こうして得られた成形体は、例えば自動車分野、OA機器分野、家電、電気・電子分野、建築分野、生活・化粧品分野、医用品分野等の種々の材料として、工業的に広く利用することができる。
A molded product can be obtained by molding the resin composition of the present invention.
Examples of the molding method include an injection molding method, an extrusion molding method, a compression molding method, a blow molding method, a calendar molding method and the like.
The molded product thus obtained can be widely used industrially as various materials in, for example, automobile fields, OA equipment fields, home appliances, electric / electronic fields, construction fields, daily life / cosmetics fields, medical supplies fields, and the like. ..

本発明の樹脂組成物、及びこれを成形した成形体は、上述した本発明の錯体化合物を含むので、白色光の下では無色透明又は薄い黄色であるが、320~380nmの波長の光を照射すると強く発光する。 Since the resin composition of the present invention and the molded product obtained by molding the same contain the complex compound of the present invention described above, the resin composition is colorless and transparent or pale yellow under white light, but is irradiated with light having a wavelength of 320 to 380 nm. Then it emits a strong light.

以下、実施例を示して本発明を詳細に説明するが、本発明は以下の記載によって限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.

[配位子の製造]
<H(3-CFsalen)の合成>
化合物(3-1)として2-ヒドロキシ-3-トリフルオロメチルベンズアルデヒド1.00g(5.29mmol)を溶解したエタノール溶液20mLに、化合物(4-1)としてエチレンジアミン0.16g(2.65mmol)を加え、30℃で1時間撹拌した。冷却後、生じた白色沈殿を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物(21-1)であるH(3-CFsalen)を収量0.99g、収率92%で得た。
[Manufacturing of ligand]
<Synthesis of H 2 (3-CF 3 salon)>
To 20 mL of an ethanol solution in which 1.00 g (5.29 mmol) of 2-hydroxy-3-trifluoromethylbenzaldehyde was dissolved as compound (3-1), 0.16 g (2.65 mmol) of ethylenediamine as compound (4-1) was added. In addition, the mixture was stirred at 30 ° C. for 1 hour. After cooling, the resulting white precipitate was collected by filtration, washed with a small amount of ethanol and dried to give compound (21-1) H 2 (3-CF 3 salon) in a yield of 0.99 g and a yield of 92%. Obtained.

Figure 0007023551000008
Figure 0007023551000008

<H(4-CFsalen)の合成>
化合物(3-2)として2-ヒドロキシ-4-トリフルオロメチルベンズアルデヒド2.00g(10.6mmol)を溶解したエタノール溶液20mLに、化合物(4-1)としてエチレンジアミン0.32g(5.3mmol)を加え、40℃で1時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物(23-1)であるH(4-CFsalen)を収量1.82g、収率84%で得た。
<Synthesis of H 2 (4-CF 3 salon)>
In 20 mL of an ethanol solution in which 2.00 g (10.6 mmol) of 2-hydroxy-4-trifluoromethylbenzaldehyde was dissolved as compound (3-2), 0.32 g (5.3 mmol) of ethylenediamine as compound (4-1) was added. In addition, the mixture was stirred at 40 ° C. for 1 hour. After cooling, the resulting white precipitate was collected by filtration, washed with a small amount of ethanol, dried, and the compound (23-1), H 2 (4-CF 3 salon), was yielded at a yield of 1.82 g and a yield of 84. Obtained in%.

Figure 0007023551000009
Figure 0007023551000009

<H(5-CFsalen)の合成>
化合物(3-3)として2-ヒドロキシ-5-トリフルオロメチルベンズアルデヒド3.80g(20mmol)を溶解したエタノール溶液50mLに、化合物(4-1)としてエチレンジアミン0.60g(10mmol)を加え、40℃で1時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物(22-1)であるH(5-CFsalen)を収量3.55g、収率88%で得た。
<Synthesis of H 2 (5-CF 3 salon)>
To 50 mL of an ethanol solution in which 3.80 g (20 mmol) of 2-hydroxy-5-trifluoromethylbenzaldehyde was dissolved as compound (3-3), 0.60 g (10 mmol) of ethylenediamine as compound (4-1) was added, and the temperature was 40 ° C. Was stirred for 1 hour. After cooling, the resulting white precipitate was collected by filtration, washed with a small amount of ethanol, dried, and the compound (22-1), H 2 (5-CF 3 salon), was yielded at 3.55 g and 88. Obtained in%.

Figure 0007023551000010
Figure 0007023551000010

<H(3-CFsal-(R,R)-stien)の合成>
化合物(3-1)として2-ヒドロキシ-3-トリフルオロメチルベンズアルデヒド1.00g(5.29mmol)を溶解したエタノール溶液20mLに、化合物(4-2)として(1R,2R)-1,2-ジフェニルエチレンジアミン0.562g(2.65mmol)を加え、40℃で1時間撹拌した。冷却後、溶液を濃縮乾固し、水100mLを加えて撹拌した。生じた白色の沈殿物を濾過により回収し、水で洗い、乾燥させ、化合物(21-2)であるH(3-CFsal-(R,R)-stien)を収量1.43g、収率97%で得た。
<Synthesis of H 2 (3-CF 3 sal- (R, R) -sien)>
(1R, 2R) -1,2- as compound (4-2) in 20 mL of ethanol solution in which 1.00 g (5.29 mmol) of 2-hydroxy-3-trifluoromethylbenzaldehyde was dissolved as compound (3-1). 0.562 g (2.65 mmol) of diphenylethylenediamine was added, and the mixture was stirred at 40 ° C. for 1 hour. After cooling, the solution was concentrated to dryness, 100 mL of water was added, and the mixture was stirred. The resulting white precipitate was collected by filtration, washed with water and dried to yield the compound (21-2) H 2 (3-CF 3 sal- (R, R) -sien) in a yield of 1.43 g. It was obtained with a yield of 97%.

Figure 0007023551000011
Figure 0007023551000011

<H(5-CFsal-(R,R)-stien)の合成>
化合物(3-3)として2-ヒドロキシ-5-トリフルオロメチルベンズアルデヒド3.80g(20mmol)を溶解したエタノール溶液50mLに、化合物(4-2)として(1R,2R)-1,2-ジフェニルエチレンジアミン2.12g(10mmol)を加え、40℃で1時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物(22-2)であるH(5-CFsal-(R,R)-stien)を収量4.65g、収率84%で得た。
<Synthesis of H 2 (5-CF 3 sal- (R, R) -sien)>
(1R, 2R) -1,2-diphenylethylenediamine as compound (4-2) in 50 mL of ethanol solution in which 3.80 g (20 mmol) of 2-hydroxy-5-trifluoromethylbenzaldehyde was dissolved as compound (3-3). 2.12 g (10 mmol) was added, and the mixture was stirred at 40 ° C. for 1 hour. After cooling, the resulting white precipitate is collected by filtration, washed with a small amount of ethanol and dried to give compound (22-2) H 2 (5-CF 3 sal- (R, R) -sien). It was obtained with a yield of 4.65 g and a yield of 84%.

Figure 0007023551000012
Figure 0007023551000012

<H(3,5-Clsalen)の合成>
化合物(3-4)として3,5-ジクロロ-2-ヒドロキシベンズアルデヒド3.82g(20mmol)を溶解したエタノール溶液50mLに、化合物(4-1)としてエチレンジアミン0.60g(10mmol)を加え、40℃で1時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物(24-1)であるH(3,5-Clsalen)を収量3.86g、収率95%で得た。
<Synthesis of H 2 (3,5-Clsalen)>
To 50 mL of an ethanol solution in which 3.82 g (20 mmol) of 3,5-dichloro-2-hydroxybenzaldehyde as compound (3-4) was dissolved, 0.60 g (10 mmol) of ethylenediamine as compound (4-1) was added, and the temperature was 40 ° C. Was stirred for 1 hour. After cooling, the resulting white precipitate was collected by filtration, washed with a small amount of ethanol and dried to yield 3.86 g of compound (24-1) H 2 (3,5-Clsalen), 95 yields. Obtained in%.

Figure 0007023551000013
Figure 0007023551000013

[実施例1]
化合物(21-1)であるH(3-CFsalen)0.404g(1mmol)と、化合物(5-1)として酢酸ユウロピウム(III)四水和物0.201g(0.5mmol)をエタノール30mLに加え、30分撹拌し、混合溶液を得た。得られた混合溶液に、化合物(6-1)としてテトラプロピルアンモニウムヒドロキシドの10質量%水溶液1.0mL(0.5mmol)加え、40℃で1時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物(1-1)である錯体化合物((C[Eu(3-CFsalen))を収量0.540g、収率94%で得た。
なお、化合物(1-1)は、前記一般式(1A)中のXが(Cであり、前記一般式(2A)及び前記一般式(2B)中のR及びRが水素原子であり、トリフルオロメチル基が3位の位置である化合物に相当する。
化合物(1-1)は白色の粉末状であり、化合物(1-1)をアセトニトリルに溶解させた溶液は無色透明であった。
化合物(1-1)のC、H、Nの各元素について元素分析を行った。結果を表1に示す。
[Example 1]
0.404 g (1 mmol) of H 2 (3-CF 3 salon) which is compound (21-1) and 0.201 g (0.5 mmol) of europium acetate (III) tetrahydrate as compound (5-1). The mixture was added to 30 mL of ethanol and stirred for 30 minutes to obtain a mixed solution. To the obtained mixed solution, 1.0 mL (0.5 mmol) of a 10 mass% aqueous solution of tetrapropylammonium hydroxide as compound (6-1) was added, and the mixture was stirred at 40 ° C. for 1 hour. After cooling, the resulting white precipitate is collected by filtration, washed with a small amount of ethanol, dried and the complex compound ((C 3 H 7 ) 4 N + [Eu (3-CF)) which is compound (1-1). 3 salen) 2 ] - ) was obtained with a yield of 0.540 g and a yield of 94%.
In the compound (1-1), X + in the general formula (1A) is (C 3 H 7 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds in which the trifluoromethyl group is at the 3-position.
Compound (1-1) was in the form of a white powder, and the solution in which compound (1-1) was dissolved in acetonitrile was colorless and transparent.
Elemental analysis was performed for each element of C, H, and N of compound (1-1). The results are shown in Table 1.

Figure 0007023551000014
Figure 0007023551000014

[実施例2]
化合物(6-1)の代わりに化合物(6-2)としてテトラブチルアンモニウムヒドロキシドの10質量%水溶液1.3mL(0.5mmol)を用いた以外は、実施例1と同様にして化合物(1-2)である錯体化合物((C[Eu(3-CFsalen))を収量0.560g、収率93%で得た。
なお、化合物(1-2)は、前記一般式(1A)中のXが(Cであり、前記一般式(2A)及び前記一般式(2B)中のR及びRが水素原子であり、トリフルオロメチル基が3位の位置である化合物に相当する。
化合物(1-2)は白色の粉末状であり、化合物(1-2)をアセトニトリルに溶解させた溶液は無色透明であった。
化合物(1-2)のC、H、Nの各元素について元素分析を行った。結果を表1に示す。
また、化合物(1-2)の0.40mm×0.30mm×0.20mmの結晶について、単結晶X線構造解析を行った。X線回折強度の測定は、単結晶X線回折装置(Bruker社製、製品名「Smart APEXII ultra」)により、線源にCu回転対陰極を用いて-100℃で行った。初期構造はSHELXS-97を用いて解き、構造の精密化はSHELXL-2013ソフトウエアパッケージを用いて行った。分子構造図を図1に示し、結晶データを以下に示す。
Crystal data:Orthorhombic,Pna2,a=23.4013(7)Å,b=10.4509(3)Å,c=43.7798(13)Å,Z=8,R=0.054。
[Example 2]
Compound (1) was used in the same manner as in Example 1 except that 1.3 mL (0.5 mmol) of a 10 mass% aqueous solution of tetrabutylammonium hydroxide was used as compound (6-2) instead of compound (6-1). -2) The complex compound ((C 4 H 9 ) 4 N + [Eu (3-CF 3 salen) 2 ] - ) was obtained with a yield of 0.560 g and a yield of 93%.
In the compound (1-2), X + in the general formula (1A) is (C 4 H 9 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds in which the trifluoromethyl group is at the 3-position.
Compound (1-2) was in the form of a white powder, and the solution in which compound (1-2) was dissolved in acetonitrile was colorless and transparent.
Elemental analysis was performed for each element of C, H, and N of compound (1-2). The results are shown in Table 1.
In addition, single crystal X-ray structure analysis was performed on the 0.40 mm × 0.30 mm × 0.20 mm crystals of compound (1-2). The X-ray diffraction intensity was measured by a single crystal X-ray diffractometer (manufactured by Bruker, product name "Smart APEXII ultra") at −100 ° C. using a Cu rotating anti-cathode as a radiation source. The initial structure was solved using SHELXS-97 and the refinement of the structure was performed using the SHELXL-2013 software package. The molecular structure diagram is shown in FIG. 1, and the crystal data is shown below.
Crystal data: Orthorhombic, Pna2 1 , a = 23.4013 (7) Å, b = 10.4059 (3) Å, c = 43.77798 (13) Å, Z = 8, R = 0.054.

Figure 0007023551000015
Figure 0007023551000015

[実施例3]
化合物(23-1)であるH(4-CFsalen)0.404g(1mmol)と、化合物(5-1)として酢酸ユウロピウム(III)四水和物0.201g(0.5mmol)をエタノール30mLに加え、30分撹拌し、混合溶液を得た。得られた混合溶液に、化合物(6-1)としてテトラプロピルアンモニウムヒドロキシドの10質量%水溶液1.0mL(0.5mmol)加え、50℃で1時間撹拌した。冷却後、混合溶液を濃縮乾固し、生じた固体を水に懸濁させた。沈殿を濾過により回収し、少量の1-プロパノールで洗い、乾燥させ、化合物(1-3)である錯体化合物((C[Eu(4-CFsalen))を収量0.384g、収率67%で得た。
なお、化合物(1-3)は、前記一般式(1A)中のXが(Cであり、前記一般式(2A)及び前記一般式(2B)中のR及びRが水素原子であり、トリフルオロメチル基が4位の位置である化合物に相当する。
化合物(1-3)は薄い黄色の粉末状であり、化合物(1-3)をアセトニトリルに溶解させた溶液は薄い黄色であった。
化合物(1-3)のC、H、Nの各元素について元素分析を行った。結果を表1に示す。
[Example 3]
0.404 g (1 mmol) of H 2 (4-CF 3 salon) which is compound (23-1) and 0.201 g (0.5 mmol) of europium acetate (III) tetrahydrate as compound (5-1). The mixture was added to 30 mL of ethanol and stirred for 30 minutes to obtain a mixed solution. To the obtained mixed solution, 1.0 mL (0.5 mmol) of a 10 mass% aqueous solution of tetrapropylammonium hydroxide as compound (6-1) was added, and the mixture was stirred at 50 ° C. for 1 hour. After cooling, the mixed solution was concentrated to dryness and the resulting solid was suspended in water. The precipitate is collected by filtration, washed with a small amount of 1-propanol, dried and complex compound ((C 3 H 7 ) 4 N + [Eu (4-CF 3 salen) 2 ] -which is compound (1-3). ) Was obtained with a yield of 0.384 g and a yield of 67%.
In the compound (1-3), X + in the general formula (1A) is (C 3 H 7 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds in which the trifluoromethyl group is at the 4-position.
Compound (1-3) was in the form of a pale yellow powder, and the solution in which compound (1-3) was dissolved in acetonitrile was pale yellow.
Elemental analysis was performed for each element of C, H, and N of compound (1-3). The results are shown in Table 1.

Figure 0007023551000016
Figure 0007023551000016

[実施例4]
化合物(6-1)の代わりに化合物(6-2)としてテトラブチルアンモニウムヒドロキシドの10質量%水溶液1.3mL(0.5mmol)を用いた以外は、実施例3と同様にして化合物(1-4)である錯体化合物((C[Eu(4-CFsalen))を収量0.468g、収率78%で得た。
なお、化合物(1-4)は、前記一般式(1A)中のXが(Cであり、前記一般式(2A)及び前記一般式(2B)中のR及びRが水素原子であり、トリフルオロメチル基が4位の位置である化合物に相当する。
化合物(1-4)は薄い黄色の粉末状であり、化合物(1-4)をアセトニトリルに溶解させた溶液は薄い黄色であった。
化合物(1-4)のC、H、Nの各元素について元素分析を行った。結果を表1に示す。
[Example 4]
Compound (1) was used in the same manner as in Example 3 except that 1.3 mL (0.5 mmol) of a 10 mass% aqueous solution of tetrabutylammonium hydroxide was used as compound (6-2) instead of compound (6-1). A complex compound ((C 4 H 9 ) 4 N + [Eu (4-CF 3 salen) 2 ] - ) which is -4) was obtained with a yield of 0.468 g and a yield of 78%.
In the compound (1-4), X + in the general formula (1A) is (C 4 H 9 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds in which the trifluoromethyl group is at the 4-position.
Compound (1-4) was in the form of a pale yellow powder, and the solution in which compound (1-4) was dissolved in acetonitrile was pale yellow.
Elemental analysis was performed for each element of C, H, and N of compound (1-4). The results are shown in Table 1.

Figure 0007023551000017
Figure 0007023551000017

[実施例5]
化合物(22-1)であるH(5-CFsalen)0.404g(1mmol)と、化合物(5-1)として酢酸ユウロピウム(III)四水和物0.201g(0.5mmol)をエタノール40mLに加え、30分撹拌し、混合溶液を得た。得られた混合溶液に、化合物(6-1)としてテトラプロピルアンモニウムヒドロキシドの10質量%水溶液1.0mL(0.5mmol)加え、40℃で1時間撹拌した。冷却後、反応溶液を濃縮して乾固し、生じた白色の粉末を少量のエタノールで洗い、乾燥させ、化合物(1-5)である錯体化合物((C[Eu(5-CFsalen))を収量0.448g、収率78%で得た。
なお、化合物(1-5)は、前記一般式(1A)中のXが(Cであり、前記一般式(2A)及び前記一般式(2B)中のR及びRが水素原子であり、トリフルオロメチル基が5位の位置である化合物に相当する。
化合物(1-5)は白色の粉末状であり、化合物(1-5)をアセトニトリルに溶解させた溶液は無色透明であった。
化合物(1-5)のC、H、Nの各元素について元素分析を行った。結果を表1に示す。
[Example 5]
0.404 g (1 mmol) of H 2 (5-CF 3 salon) which is compound (22-1) and 0.201 g (0.5 mmol) of europium acetate (III) tetrahydrate as compound (5-1). The mixture was added to 40 mL of ethanol and stirred for 30 minutes to obtain a mixed solution. To the obtained mixed solution, 1.0 mL (0.5 mmol) of a 10 mass% aqueous solution of tetrapropylammonium hydroxide as compound (6-1) was added, and the mixture was stirred at 40 ° C. for 1 hour. After cooling, the reaction solution is concentrated to dryness, the resulting white powder is washed with a small amount of ethanol, dried, and the complex compound ((C 3 H 7 ) 4 N + [Eu) which is compound (1-5). (5-CF 3 salen) 2 ] - ) was obtained with a yield of 0.448 g and a yield of 78%.
In the compound (1-5), X + in the general formula (1A) is (C 3 H 7 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds in which the trifluoromethyl group is at the 5-position.
Compound (1-5) was in the form of a white powder, and the solution in which compound (1-5) was dissolved in acetonitrile was colorless and transparent.
Elemental analysis was performed for each element of C, H, and N of compound (1-5). The results are shown in Table 1.

Figure 0007023551000018
Figure 0007023551000018

[実施例6]
化合物(22-1)であるH(5-CFsalen)0.404g(1mmol)と、化合物(5-1)として酢酸ユウロピウム(III)四水和物0.201g(0.5mmol)をエタノール40mLに加え、30分撹拌し、混合溶液を得た。得られた混合溶液に、化合物(6-2)としてテトラブチルアンモニウムヒドロキシドの10質量%水溶液1.3mL(0.5mmol)加え、40℃で1時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物(1-6)である錯体化合物((C[Eu(5-CFsalen))を収量0.518g、収率87%で得た。
なお、化合物(1-6)は、前記一般式(1A)中のXが(Cであり、前記一般式(2A)及び前記一般式(2B)中のR及びRが水素原子であり、トリフルオロメチル基が5位の位置である化合物に相当する。
化合物(1-6)は白色の粉末状であり、化合物(1-6)をアセトニトリルに溶解させた溶液は無色透明であった。
化合物(1-6)のC、H、Nの各元素について元素分析を行った。結果を表1に示す。
また、化合物(1-6)の0.45mm×0.25mm×0.10mmの結晶について、単結晶X線構造解析を行った。X線回折強度の測定は、単結晶X線構造解析装置(株式会社リガク製、製品名「R-AXIS RAPID」)により、線源にMo封入管を用いて25℃で行った。初期構造はSHELXS-97を用いて解き、構造の精密化はSHELXL-97ソフトウエアパッケージを用いて行った。分子構造図を図2に示し、結晶データを以下に示す。
Crystal data:Monoclinic,P2/c,a=12.1611(3)Å,b=21.0789(5)Å,c=21.8826(5)Å,β=90.018(1)°,Z=4,R=0.055。
[Example 6]
0.404 g (1 mmol) of H 2 (5-CF 3 salon) which is compound (22-1) and 0.201 g (0.5 mmol) of europium acetate (III) tetrahydrate as compound (5-1). The mixture was added to 40 mL of ethanol and stirred for 30 minutes to obtain a mixed solution. To the obtained mixed solution, 1.3 mL (0.5 mmol) of a 10 mass% aqueous solution of tetrabutylammonium hydroxide as compound (6-2) was added, and the mixture was stirred at 40 ° C. for 1 hour. After cooling, the resulting white precipitate is collected by filtration, washed with a small amount of ethanol, dried and the complex compound ((C 4 H 9 ) 4 N + [Eu (5-CF)) which is compound (1-6). 3 salen) 2 ] - ) was obtained with a yield of 0.518 g and a yield of 87%.
In the compound (1-6), X + in the general formula (1A) is (C 4 H 9 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds in which the trifluoromethyl group is at the 5-position.
Compound (1-6) was in the form of a white powder, and the solution in which compound (1-6) was dissolved in acetonitrile was colorless and transparent.
Elemental analysis was performed for each element of C, H, and N of compound (1-6). The results are shown in Table 1.
In addition, single crystal X-ray structure analysis was performed on 0.45 mm × 0.25 mm × 0.10 mm crystals of compound (1-6). The X-ray diffraction intensity was measured by a single crystal X-ray structure analyzer (manufactured by Rigaku Co., Ltd., product name "R-AXIS RAPID") at 25 ° C. using a Mo-encapsulated tube as a radiation source. The initial structure was solved using SHELXS-97 and the refinement of the structure was performed using the SHELXL-97 software package. The molecular structure diagram is shown in FIG. 2, and the crystal data is shown below.
Crystal data: Monoclinic, P2 1 / c, a = 12.1611 (3) Å, b = 21.0789 (5) Å, c = 21.8826 (5) Å, β = 90.188 (1) °, Z = 4, R = 0.055.

Figure 0007023551000019
Figure 0007023551000019

[実施例7]
化合物(21-2)であるH(3-CFsal-(R,R)-stien)0.555g(1mmol)と、化合物(5-1)として酢酸ユウロピウム(III)四水和物0.201g(0.5mmol)をエタノール50mLに加え、30分撹拌し、混合溶液を得た。得られた混合溶液に、化合物(6-3)としてテトラブチルアンモニウムブロミド0.960g(3mmol)と、化合物(6-4)としてトリエチルアミン0.5mLを加え、50℃で1時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物(1-7)である錯体化合物((C[Eu(3-CFsal-(R,R)-stien))を収量0.614g、収率82%で得た。
なお、化合物(1-7)は、前記一般式(1A)中のXが(Cであり、前記一般式(2A)及び前記一般式(2B)中のR及びRがフェニル基であり、トリフルオロメチル基が3位の位置である化合物に相当する。
化合物(1-7)は白色の粉末状であり、化合物(1-7)をアセトニトリルに溶解させた溶液は無色透明であった。
化合物(1-7)のC、H、Nの各元素について元素分析を行った。結果を表1に示す。
[Example 7]
Compound (21-2) H 2 (3-CF 3 sal- (R, R) -sien) 0.555 g (1 mmol) and Europium acetate (III) tetrahydrate 0 as compound (5-1) .201 g (0.5 mmol) was added to 50 mL of ethanol and stirred for 30 minutes to give a mixed solution. To the obtained mixed solution, 0.960 g (3 mmol) of tetrabutylammonium bromide as compound (6-3) and 0.5 mL of triethylamine as compound (6-4) were added, and the mixture was stirred at 50 ° C. for 1 hour. After cooling, the resulting white precipitate is collected by filtration, washed with a small amount of ethanol, dried and the complex compound ((C 4 H 9 ) 4 N + [Eu (3-CF)) which is compound (1-7). 3 sal- (R, R) -steen) 2 ] - ) was obtained with a yield of 0.614 g and a yield of 82%.
In the compound (1-7), X + in the general formula (1A) is (C 4 H 9 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 correspond to the compound in which the phenyl group is located and the trifluoromethyl group is in the 3-position position.
Compound (1-7) was in the form of a white powder, and the solution in which compound (1-7) was dissolved in acetonitrile was colorless and transparent.
Elemental analysis was performed for each element of C, H, and N of compound (1-7). The results are shown in Table 1.

Figure 0007023551000020
Figure 0007023551000020

[実施例8]
化合物(22-2)であるH(5-CFsal-(R,R)-stien)0.555g(1mmol)と、化合物(5-1)として酢酸ユウロピウム(III)四水和物0.201g(0.5mmol)をエタノール50mLに加え、30分撹拌し、混合溶液を得た。得られた混合溶液に、化合物(6-3)としてテトラブチルアンモニウムブロミド0.960g(3mmol)と、化合物(6-4)としてトリエチルアミン0.5mLとを加え、50℃で1時間撹拌した。冷却後、反応溶液を濃縮して乾固した後に水を加え、クリーム色の沈殿物を得た。沈殿物を濾過により回収し、水で洗い、乾燥させ、化合物(1-8)である錯体化合物((C[Eu(5-CFsal-(R,R)-stien))を収量0.666g、収率88%で得た。
なお、化合物(1-8)は、前記一般式(1A)中のXが(Cであり、前記一般式(2A)及び前記一般式(2B)中のR及びRがフェニル基であり、トリフルオロメチル基が5位の位置である化合物に相当する。
化合物(1-8)はクリーム色の粉末状であるが、化合物(1-8)をアセトニトリルに溶解させた溶液は無色透明であった。
化合物(1-8)のC、H、Nの各元素について元素分析を行った。結果を表1に示す。
[Example 8]
0.555 g (1 mmol) of H 2 (5-CF 3 sal- (R, R) -sien) which is compound (22-2) and europium (III) tetrahydrate tetrahydrate 0 as compound (5-1). .201 g (0.5 mmol) was added to 50 mL of ethanol and stirred for 30 minutes to give a mixed solution. To the obtained mixed solution, 0.960 g (3 mmol) of tetrabutylammonium bromide as compound (6-3) and 0.5 mL of triethylamine as compound (6-4) were added, and the mixture was stirred at 50 ° C. for 1 hour. After cooling, the reaction solution was concentrated and dried, and then water was added to obtain a cream-colored precipitate. The precipitate is collected by filtration, washed with water, dried, and the complex compound ((C 4 H 9 ) 4 N + [Eu (5-CF 3 sal- (R, R)-) which is compound (1-8). Steen) 2 ] - ) was obtained with a yield of 0.666 g and a yield of 88%.
In the compound (1-8), X + in the general formula (1A) is (C 4 H 9 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are phenyl groups, and the trifluoromethyl group is at the 5-position position, which corresponds to the compound.
Compound (1-8) was in the form of a cream-colored powder, but the solution in which compound (1-8) was dissolved in acetonitrile was colorless and transparent.
Elemental analysis was performed for each element of C, H, and N of compound (1-8). The results are shown in Table 1.

Figure 0007023551000021
Figure 0007023551000021

[比較例1]
化合物(24-1)であるH(3,5-Clsalen)0.406g(1mmol)と、化合物(5-1)として酢酸ユウロピウム(III)四水和物0.201g(0.5mmol)をエタノール40mLに加え、1時間撹拌し、混合溶液を得た。得られた混合溶液に、化合物(6-4)としてトリエチルアミン1mLを加え、60℃で1時間撹拌した。冷却後、生じたクリーム色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物(1-9)である錯体化合物((CNH[Eu(3,5-Clsalen))を収率94%で得た。
なお、化合物(1-9)は、前記一般式(1A)中のXが(CNHであり、前記一般式(2A)及び前記一般式(2B)中のR及びRが水素原子であり、トリフルオロメチル基の代わりにClを3位と5位の位置に有する化合物に相当する。
化合物(1-9)はクリーム色の粉末状であり、化合物(1-9)をアセトニトリルに溶解させた溶液は薄い黄色であった。
化合物(1-9)のC、H、Nの各元素について元素分析を行った。結果を表1に示す。
[Comparative Example 1]
0.406 g (1 mmol) of H 2 (3,5-Clsalen), which is compound (24-1), and 0.201 g (0.5 mmol) of europium acetate (III) tetrahydrate as compound (5-1). The mixture was added to 40 mL of ethanol and stirred for 1 hour to obtain a mixed solution. To the obtained mixed solution, 1 mL of triethylamine as compound (6-4) was added, and the mixture was stirred at 60 ° C. for 1 hour. After cooling, the resulting cream-colored precipitate is collected by filtration, washed with a small amount of ethanol, dried, and the complex compound ((C 2 H 5 ) 3 NH + [Eu (3, 3)) which is compound (1-9). 5-Clsalen) 2 ] - ) was obtained in a yield of 94%.
In the compound (1-9), X + in the general formula (1A) is (C 2 H 5 ) 3 NH + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds having Cl at the 3rd and 5th positions instead of the trifluoromethyl group.
Compound (1-9) was in the form of a cream-colored powder, and the solution of compound (1-9) in acetonitrile was pale yellow.
Elemental analysis was performed for each element of C, H, and N of compound (1-9). The results are shown in Table 1.

Figure 0007023551000022
Figure 0007023551000022

[比較例2]
化合物(24-1)であるH(3,5-Clsalen)0.406g(1mmol)と、化合物(5-1)として酢酸ユウロピウム(III)四水和物0.201g(0.5mmol)をメタノール40mLに加え、1時間撹拌し、混合溶液を得た。得られた混合溶液に、化合物(6-5)としてテトラエチルアンモニウムヒドロキシドの10質量%水溶液0.74mL(0.5mmol)加え、60℃で1時間撹拌した。冷却後、生じたクリーム色の沈殿物を濾過により回収し、少量のメタノールで洗い、乾燥させ、化合物(1-10)である錯体化合物((C[Eu(3,5-Clsalen))を収率81%で得た。
なお、化合物(1-10)は、前記一般式(1A)中のXが(Cであり、前記一般式(2A)及び前記一般式(2B)中のR及びRが水素原子であり、トリフルオロメチル基の代わりにClを3位と5位の位置に有する化合物に相当する。
化合物(1-10)はクリーム色の粉末状であり、化合物(1-10)をアセトニトリルに溶解させた溶液は薄い黄色であった。
化合物(1-10)のC、H、Nの各元素について元素分析を行った。結果を表1に示す。
[Comparative Example 2]
0.406 g (1 mmol) of H 2 (3,5-Clsalen), which is compound (24-1), and 0.201 g (0.5 mmol) of europium acetate (III) tetrahydrate as compound (5-1). The mixture was added to 40 mL of methanol and stirred for 1 hour to obtain a mixed solution. To the obtained mixed solution, 0.74 mL (0.5 mmol) of a 10 mass% aqueous solution of tetraethylammonium hydroxide as compound (6-5) was added, and the mixture was stirred at 60 ° C. for 1 hour. After cooling, the resulting cream-colored precipitate is collected by filtration, washed with a small amount of methanol, dried, and the complex compound ((C 2 H 5 ) 4 N + [Eu (3, 3)) which is compound (1-10). 5-Clsalen) 2 ] - ) was obtained in a yield of 81%.
In the compound (1-10), X + in the general formula (1A) is (C 2 H 5 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds having Cl at the 3rd and 5th positions instead of the trifluoromethyl group.
Compound (1-10) was in the form of a cream-colored powder, and the solution of compound (1-10) in acetonitrile was pale yellow.
Elemental analysis was performed for each element of C, H, and N of compound (1-10). The results are shown in Table 1.

Figure 0007023551000023
Figure 0007023551000023

Figure 0007023551000024
Figure 0007023551000024

[測定・評価]
<吸収スペクトルの測定>
実施例6で得られた錯体化合物(化合物(1-6))、及び比較例1で得られた錯体化合物(化合物(1-9))を、それぞれ濃度が2.0×10-5mol/Lとなるようにアセトニトリルに溶解させた。得られた各アセトニトリル溶液について、分光光度計(日本分光株式会社製、製品名「V-570」)を用いて吸収スペクトルを測定した。結果を図3に示す。
また、実施例2で得られた錯体化合物(化合物(1-2))、及び実施例4で得られた錯体化合物(化合物(1-4))を濃度が2.0×10-5mol/Lとなるようにアセトニトリルに溶解させた。得られたアセトニトリル溶液について、分光光度計(日本分光株式会社製、製品名「V-570」)を用いて吸収スペクトルを測定した。結果を図4に示す。なお、図4には、実施例6で得られた錯体化合物のアセトニトリル溶液の吸収スペクトルの結果も示す。
[Measurement / evaluation]
<Measurement of absorption spectrum>
The complex compound (compound (1-6)) obtained in Example 6 and the complex compound (compound (1-9)) obtained in Comparative Example 1 each had a concentration of 2.0 × 10-5 mol /. It was dissolved in acetonitrile so as to be L. The absorption spectrum of each of the obtained acetonitrile solutions was measured using a spectrophotometer (manufactured by JASCO Corporation, product name "V-570"). The results are shown in FIG.
Further, the complex compound (compound (1-2)) obtained in Example 2 and the complex compound (compound (1-4)) obtained in Example 4 had a concentration of 2.0 × 10-5 mol /. It was dissolved in acetonitrile so as to be L. The absorption spectrum of the obtained acetonitrile solution was measured using a spectrophotometer (manufactured by JASCO Corporation, product name "V-570"). The results are shown in FIG. In addition, FIG. 4 also shows the result of the absorption spectrum of the acetonitrile solution of the complex compound obtained in Example 6.

図3から明らかなように、実施例6で得られた錯体化合物のアセトニトリル溶液の吸収スペクトルを測定したところ、337nmに配位子のπ-π遷移に由来する吸収帯のピークがあることが分かった。その吸収帯の裾野は400nm付近まで広がっているが、可視領域(400~900nm)にはかかっておらず、アセトニトリル溶液の色は無色透明であった。
一方、比較例1で得られた錯体化合物のアセトニトリル溶液の吸収スペクトルでは、359nmに配位子のπ-π遷移に由来する吸収帯のピークがある。そして、その吸収帯の裾野は可視領域の400nm以上の波長まで広がっており、アセトニトリル溶液の色は薄い黄色であった。
As is clear from FIG. 3, when the absorption spectrum of the acetonitrile solution of the complex compound obtained in Example 6 was measured, it was found that there was a peak in the absorption band derived from the π-π * transition of the ligand at 337 nm. Do you get it. The base of the absorption band extended to around 400 nm, but did not cover the visible region (400 to 900 nm), and the color of the acetonitrile solution was colorless and transparent.
On the other hand, in the absorption spectrum of the acetonitrile solution of the complex compound obtained in Comparative Example 1, there is a peak of the absorption band derived from the π-π * transition of the ligand at 359 nm. The base of the absorption band extended to a wavelength of 400 nm or more in the visible region, and the color of the acetonitrile solution was pale yellow.

また、図4から明らかなように、実施例2、4、6で得られた錯体化合物において、配位子のπ-π遷移に由来する吸収帯のピークは配位子のベンゼン環上にあるトリフルオロメチル基の位置によって異なることが分かった。すなわち、化合物(1-6)のπ-π吸収帯のピークが337nmと最も短波長であり、化合物(1-4)のπ-π吸収帯のピークが352nmと最も長波長であった。化合物(1-2)のπ-π吸収帯のピークは343nmであり、化合物(1-6)及び化合物(1-4)の中間にあった。この吸収波長の違いは、電子吸引基であるトリフルオロメチル基の電子的影響によるものと考えられる。また、これらの化合物の固体粉末の色は、化合物(1-2)と化合物(1-6)が白色であり、化合物(1-4)が薄い黄色であり、吸収スペクトルの結果と一致している。 Further, as is clear from FIG. 4, in the complex compounds obtained in Examples 2, 4 and 6, the peak of the absorption band derived from the π-π * transition of the ligand is on the benzene ring of the ligand. It was found that it depends on the position of a certain trifluoromethyl group. That is, the peak of the π-π * absorption band of compound (1-6) was the shortest wavelength of 337 nm, and the peak of the π-π * absorption band of compound (1-4) was the longest wavelength of 352 nm. .. The peak of the π-π * absorption band of compound (1-2) was 343 nm, which was between compound (1-6) and compound (1-4). This difference in absorption wavelength is considered to be due to the electronic influence of the trifluoromethyl group, which is an electron-withdrawing group. In addition, the color of the solid powder of these compounds was white for compound (1-2) and compound (1-6) and light yellow for compound (1-4), which was consistent with the result of the absorption spectrum. There is.

<発光特性の評価>
(発光スペクトルの測定1)
実施例6で得られた錯体化合物を濃度が2.0×10-6mol/Lとなるようにアセトニトリルに溶解させた。得られたアセトニトリル溶液について、分光蛍光光度計(株式会社日立製作所製、製品名「F-7000」)を用い、励起波長337nmで溶液の発光スペクトルを測定した。結果を図5に示す。
<Evaluation of light emission characteristics>
(Measurement of emission spectrum 1)
The complex compound obtained in Example 6 was dissolved in acetonitrile so as to have a concentration of 2.0 × 10 -6 mol / L. With respect to the obtained acetonitrile solution, the emission spectrum of the solution was measured at an excitation wavelength of 337 nm using a spectrofluorometer (manufactured by Hitachi, Ltd., product name “F-7000”). The results are shown in FIG.

また、実施例6で得られた錯体化合物について、分光蛍光光度計(株式会社日立製作所製、製品名「F-7000」)を用い、励起波長337nmで固体の発光スペクトルを測定した。結果を図6に示す。 Further, for the complex compound obtained in Example 6, the emission spectrum of a solid was measured at an excitation wavelength of 337 nm using a spectrofluorometer (manufactured by Hitachi, Ltd., product name “F-7000”). The results are shown in FIG.

(発光スペクトルの測定2)
実施例2、4、6~8で得られた錯体化合物、及び比較例1、2で得られた錯体化合物を用い、キャスト法により以下のようにしてフィルムを作製した。
直径5.5cmのアルミカップ中で錯体化合物0.005mmolをジクロロメタン30mLに溶解させた後、撹拌しながらポリメチルメタクリレート(PMMA)1.00gを加えて溶解させ、混合溶液を得た。得られた混合溶液を30℃で24時間放置することでジクロロメタンを蒸発させて、厚さ0.32±0.02mmのフィルムを得た。
得られたフィルムを縦8.8mm、横8.8mmの大きさに切断し、積分球を搭載した分光蛍光光度計(株式会社日立製作所製、製品名「F-7000」)を用い、励起波長365nmで発光スペクトルを同一条件(同一の電圧、スリット幅)において測定した。
実施例6で得られた錯体化合物を含むフィルムの発光スペクトルを図7に示す。
実施例2、7で得られた錯体化合物、及び比較例1、2で得られた錯体化合物を含むフィルムの発光スペクトルを図8に示す。
実施例4、8で得られた錯体化合物、及び比較例1で得られた錯体化合物を含むフィルムの発光スペクトルを図9に示す。
(Measurement of emission spectrum 2)
Using the complex compounds obtained in Examples 2, 4, 6 to 8 and the complex compounds obtained in Comparative Examples 1 and 2, a film was prepared as follows by a casting method.
After dissolving 0.005 mmol of the complex compound in 30 mL of dichloromethane in an aluminum cup having a diameter of 5.5 cm, 1.00 g of polymethylmethacrylate (PMMA) was added and dissolved with stirring to obtain a mixed solution. Dichloromethane was evaporated by leaving the obtained mixed solution at 30 ° C. for 24 hours to obtain a film having a thickness of 0.32 ± 0.02 mm.
The obtained film was cut into a size of 8.8 mm in length and 8.8 mm in width, and an excitation wavelength was used using a spectral fluorometer (manufactured by Hitachi, Ltd., product name "F-7000") equipped with an integrating sphere. The emission spectrum was measured at 365 nm under the same conditions (same voltage, slit width).
The emission spectrum of the film containing the complex compound obtained in Example 6 is shown in FIG.
The emission spectrum of the film containing the complex compound obtained in Examples 2 and 7 and the complex compound obtained in Comparative Examples 1 and 2 is shown in FIG.
The emission spectra of the film containing the complex compound obtained in Examples 4 and 8 and the complex compound obtained in Comparative Example 1 are shown in FIG.

(量子収率の測定)
実施例2、4、6~8で得られた錯体化合物を、それぞれ濃度が2.0×10-6mol/Lとなるように溶媒に溶解させた。得られた各溶液について、絶対PL量子収率測定装置(浜松ホトニクス株式会社製、製品名「Quantaurus-QY C11347-01」)を用い、絶対法で溶液の量子収率を励起波長365nmで測定した。結果を表2に示す。なお、溶媒としては、アセトニトリル、DMSO(ジメチルスルホキシド)、DMF(N,N-ジメチルホルムアミド)、アセトンのいずれかを用いた。結果を表2に示す。
(Measurement of quantum yield)
The complex compounds obtained in Examples 2, 4, 6 to 8 were dissolved in a solvent so as to have a concentration of 2.0 × 10-6 mol / L, respectively. For each of the obtained solutions, the quantum yield of the solution was measured at an excitation wavelength of 365 nm by an absolute method using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., product name "Quantaurus-QY C11347-01"). .. The results are shown in Table 2. As the solvent, any one of acetonitrile, DMSO (dimethyl sulfoxide), DMF (N, N-dimethylformamide), and acetone was used. The results are shown in Table 2.

一方、比較例1、2で得られた錯体化合物については、以下のようにして量子収率を測定した。
まず、比較例1で得られた錯体化合物を濃度が2.0×10-6mol/Lとなるようにアセトニトリルに溶解させた。得られたアセトニトリル溶液について、積分球を搭載した分光蛍光光度計(株式会社日立製作所製、製品名「F-7000」)を用い、絶対法で溶液の量子収率を励起波長365nmで測定した。
次いで、比較例1で得られた錯体化合物を濃度が2.0×10-6mol/LとなるようにDMSO、DMF、アセトンのいずれかの溶媒に溶解させた。得られた各溶液の量子収率を、比較例1のアセトニトリル溶液の量子収率の値(0.24)を基準として、相対法により求めた。結果を表2に示す。
また、比較例2で得られた錯体化合物を濃度が2.0×10-6mol/Lとなるようにアセトニトリル、DMSO、DMF、アセトンのいずれかの溶媒に溶解させた。得られた各溶液の量子収率を、比較例1のアセトニトリル溶液の量子収率の値(0.24)を基準として、相対法により求めた。結果を表2に示す。
On the other hand, for the complex compounds obtained in Comparative Examples 1 and 2, the quantum yields were measured as follows.
First, the complex compound obtained in Comparative Example 1 was dissolved in acetonitrile so as to have a concentration of 2.0 × 10 -6 mol / L. With respect to the obtained acetonitrile solution, the quantum yield of the solution was measured at an excitation wavelength of 365 nm by an absolute method using a spectrofluorometer equipped with an integrating sphere (manufactured by Hitachi, Ltd., product name “F-7000”).
Then, the complex compound obtained in Comparative Example 1 was dissolved in any solvent of DMSO, DMF, or acetone so as to have a concentration of 2.0 × 10 -6 mol / L. The quantum yield of each of the obtained solutions was determined by a relative method with reference to the quantum yield value (0.24) of the acetonitrile solution of Comparative Example 1. The results are shown in Table 2.
Further, the complex compound obtained in Comparative Example 2 was dissolved in any solvent of acetonitrile, DMSO, DMF or acetone so as to have a concentration of 2.0 × 10 -6 mol / L. The quantum yield of each of the obtained solutions was determined by a relative method with reference to the quantum yield value (0.24) of the acetonitrile solution of Comparative Example 1. The results are shown in Table 2.

Figure 0007023551000025
Figure 0007023551000025

実施例6で得られた錯体化合物(化合物(1-6))は、ブラックライト波長(365nm)付近の紫外線を照射すると、固体状及び溶液中のいずれにおいても赤色に発光した。図5は化合物(1-6)の溶液中での発光スペクトルであり、図6は化合物(1-6)の固体の発光スペクトルであり、図7は化合物(1-6)を含むフィルムの発光スペクトルである。これら図5~7から明らかなように、化合物(1-6)は614nmに半値幅の狭いシャープな発光バンドを有する。
一方、比較例1で得られた錯体化合物(化合物(1-9))も、ブラックライト波長(365nm)付近の紫外線を照射すると、固体状及び溶液中のいずれにおいても赤色に発光した。また、化合物(1-9)の発光スペクトルも、化合物(1-6)の発光スペクトルと同様なスペクトルパターンを示す。
しかし、表2から明らかなように、化合物(1-6)と、化合物(1-9)の溶液の量子収率を比較したところ、化合物(1-6)の量子収率の値は、いずれも化合物(1-9)よりも高かった。
実施例2、4、7、8で得られた錯体化合物についても、量子収率の値は比較例1、2で得られた錯体化合物より高かった。
また、実施例2、4、6~8で得られた錯体化合物、及び比較例1、2で得られた錯体化合物を用いてフィルムを作製し、その発光スペクトルを測定したところ、図7~9に示すように、実施例2、4、6~8で得られた錯体化合物を含むフィルムの方が、比較例1、2で得られた錯体化合物を含むフィルムに比べて発光強度が高かった。
以上の結果より、実施例2、4、6~8で得られた錯体化合物の方が比較例1、2で得られた錯体化合物よりも蛍光材料として優れていることが示された。実施例1、3、5で得られた錯体化合物も、実施例2、4、6で得られた錯体化合物と同様の効果を有する。
The complex compound (compound (1-6)) obtained in Example 6 emitted red light in both solid form and in solution when irradiated with ultraviolet rays near the black light wavelength (365 nm). FIG. 5 is an emission spectrum of compound (1-6) in a solution, FIG. 6 is an emission spectrum of a solid of compound (1-6), and FIG. 7 is emission of a film containing compound (1-6). It is a spectrum. As is clear from these FIGS. 5 to 7, compound (1-6) has a sharp emission band having a narrow half width at 614 nm.
On the other hand, the complex compound (compound (1-9)) obtained in Comparative Example 1 also emitted red light in both solid form and in solution when irradiated with ultraviolet rays near the black light wavelength (365 nm). Further, the emission spectrum of the compound (1-9) also shows a spectrum pattern similar to the emission spectrum of the compound (1-6).
However, as is clear from Table 2, when the quantum yields of the solutions of the compound (1-6) and the compound (1-9) are compared, the value of the quantum yield of the compound (1-6) is eventually determined. Was also higher than compound (1-9).
The quantum yield values of the complex compounds obtained in Examples 2, 4, 7 and 8 were also higher than those of the complex compounds obtained in Comparative Examples 1 and 2.
Further, when a film was prepared using the complex compounds obtained in Examples 2, 4, 6 to 8 and the complex compounds obtained in Comparative Examples 1 and 2, and the emission spectra thereof were measured, FIGS. 7 to 9 were taken. As shown in the above, the films containing the complex compounds obtained in Examples 2, 4, 6 to 8 had higher emission intensities than the films containing the complex compounds obtained in Comparative Examples 1 and 2.
From the above results, it was shown that the complex compounds obtained in Examples 2, 4, 6 to 8 are superior to the complex compounds obtained in Comparative Examples 1 and 2 as a fluorescent material. The complex compounds obtained in Examples 1, 3 and 5 have the same effects as the complex compounds obtained in Examples 2, 4 and 6.

本発明の錯体化合物は発光強度が高く、例えばインビジブルインク、発光標識試薬、有機EL素子、太陽電池の波長変換材料、白色LED等の発光材料として好適である。 The complex compound of the present invention has high emission intensity and is suitable as a light emitting material such as an invisible ink, a light emitting reagent, an organic EL element, a wavelength conversion material for a solar cell, and a white LED.

Claims (3)

下記一般式(1)で表される、錯体化合物
Figure 0007023551000026
式(1A)中、O 11 -A 11 -N 11 -A 12 -N 12 -A 13 -O 12 は下記一般式(2A)であり、O 21 -A 21 -N 21 -A 22 -N 22 -A 23 -O 22 は下記一般式(2B)であり、X は対カチオンである。
Figure 0007023551000027
式(2A)及び式(2B)中、R 及びR は各々独立に、水素原子、メチル基、フェニル基である。なお、式(2A)において、O 11 とO 12 とN 11 とN 12 のEuと結合する結合手は省略する。式(2B)において、O 21 とO 22 とN 21 とN 22 のEuと結合する結合手は省略する。
A complex compound represented by the following general formula (1 A ) .
Figure 0007023551000026
In the formula (1A), O 11 -A 11 - N 11 -A 12 - N 12 -A 13 - O 12 is the following general formula (2A), and is O 21 -A 21 - N 21 -A 22 - N 22 . -A 23 - O 22 is the following general formula (2B), and X + is a counter cation.
Figure 0007023551000027
In formulas (2A) and (2B), R 1 and R 2 are independently hydrogen atoms, methyl groups, and phenyl groups, respectively. In the formula (2A), the bond that binds Eu of O 11 and O 12 and N 11 and N 12 is omitted. In formula (2B), the bond that binds Eu of O 21 and O 22 and N 21 and N 22 is omitted.
請求項1に記載の錯体化合物を含む、インク。 An ink containing the complex compound according to claim 1. 請求項1に記載の錯体化合物を含む、樹脂組成物。 A resin composition containing the complex compound according to claim 1.
JP2021068103A 2021-04-14 2021-04-14 Complex compounds, inks and resin compositions Active JP7023551B1 (en)

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