JP5735791B2 - Device containing metal complex - Google Patents

Description

  The present invention relates to a device including a metal complex of cerium and a nitrogen atom-containing cyclic compound.

  A cyclic compound (crown ether) containing an oxygen atom in the skeleton is a compound that can strongly trap various ions. It has been reported that a complex in which cerium ions are incorporated into crown ether exhibits light emission based on the 5d-4f transition of cerium ions, and its application as an organic EL material has been studied (Non-patent Document 1).

T. T. et al. Yu et al. Solid-State Electronics. 51, 894-899 (2007).

  However, in the conventional cerium complex using the crown ether described in Non-Patent Document 1, the maximum emission spectrum (emission peak) is located in the ultraviolet region, and it is difficult to use in display applications and illumination applications. There was a problem. An object of the present invention is to provide a cerium complex whose emission peak is located in the visible light region and sufficiently emits light in the visible light region, and further to provide an element that sufficiently emits light in the visible light region using this complex. is there.

  In order to solve the above-described problems, the present inventors have conducted intensive research and have completed the present invention. That is, the present invention provides the following [1] to [10].

（式中、Ａ¹は、置換基を有していてもよいヒドロカーボンジイル基を表す。複数あるＡ¹はそれぞれ同一であっても異なっていてもよい。ｎは３以上の整数を表す。Ｚ¹は、−Ｏ−、−Ｓ−、−ＮＲ¹−、又は−ＰＲ²−を表すが、１つ以上は−ＮＲ¹−である。複数あるＺ¹はそれぞれ同一であっても異なっていてもよい。Ｒ¹及びＲ²は、水素原子、又は置換基を有していてもよいヒドロカルビル基を表す。Ｒ¹及びＲ²はそれぞれ同一であっても異なっていてもよい。Ｒ¹が複数ある場合、複数のＲ¹はそれぞれ同一であっても異なっていてもよい。Ｒ²が複数ある場合、複数のＲ²はそれぞれ同一であっても異なっていてもよい。）
［２］Ａ¹、Ｒ¹又はＲ²が、置換基として１つ以上の窒素原子含有ヘテロシクリル基を有する上記［１］に記載の素子。
［３］窒素原子含有環式化合物が下記式（２）で表される、上記［１］又は［２］に記載の素子。

（式中、Ａ²及びＡ³は、置換基を有していてもよいヒドロカーボンジイル基を表す。Ａ²及びＡ³はそれぞれ同一であっても異なっていてもよい。Ａ²が複数ある場合、複数のＡ²はそれぞれ同一であっても異なっていてもよい。Ａ³が複数ある場合、複数のＡ³はそれぞれ同一であっても異なっていてもよい。Ｚ²は、−Ｏ−、−Ｓ−、−ＮＲ¹−、又は−ＰＲ²−を表す。Ｚ²が複数ある場合、複数のＺ²はそれぞれ同一であっても異なっていてもよい。ｍは１以上の整数を表し、ｐは０以上の整数を表し、ｍ＋ｐは３以上の整数である。Ｒ¹⁰は置換基を有していてもよいヒドロカーボンジイル基を表す。Ｒ¹⁰が複数ある場合、複数のＲ¹⁰はそれぞれ同一であっても異なっていてもよい。Ｌ¹⁰は、置換基を有していてもよい窒素原子含有ヘテロシクリル基を表す。Ｌ¹⁰が複数ある場合、複数のＬ¹⁰はそれぞれ同一であっても異なっていてもよい。）
［４］上記式（２）において、ｍ＋ｐが３〜６の整数である上記［３］に記載の素子。
［５］上記式（２）において、ｐが０である上記［３］又は［４］に記載の素子。
［６］窒素原子含有環式化合物が下記式（３）で表される、上記［１］〜［５］のいずれか１項に記載の素子。

（式中、Ｌ¹¹、Ｌ¹²、Ｌ¹³及びＬ¹⁴は、置換基を有していてもよい窒素原子含有ヘテロシクリル基を表す。Ｌ¹¹、Ｌ¹²、Ｌ¹³及びＬ¹⁴はそれぞれ同一であっても異なっていてもよい。Ａ¹¹、Ａ¹²、Ａ¹³及びＡ¹⁴は、置換基を有していてもよいヒドロカーボンジイル基を表す。Ａ¹¹、Ａ¹²、Ａ¹³及びＡ¹⁴はそれぞれ同一であっても異なっていてもよい。Ｒ¹¹、Ｒ¹²、Ｒ¹³及びＲ¹⁴は、置換基を有していてもよいヒドロカーボンジイル基を表す。Ｒ¹¹、Ｒ¹²、Ｒ¹³及びＲ¹⁴はそれぞれ同一であっても異なっていてもよい。）
［７］上記金属錯体が、下記組成式（１１）で表される金属錯体である［６］に記載の素子。

（式中、Ｌは上記式（３）で表される窒素原子含有環式化合物を表す。Ｌが複数ある場合、複数のＬはそれぞれ同一であっても異なっていてもよい。Ｘは対イオンを表す。Ｘが複数ある場合、複数のＸはそれぞれ同一であっても異なっていてもよい。Ｌ’は上記式（３）で表される窒素原子含有環式化合物以外の２座以下の配位子を表す。ａ’は正の数であり、ｂ’及びｃ’は０以上の数である。ｂ’及びｃ’はそれぞれ同一であっても異なっていてもよい。）
［８］上記素子が電界発光素子である上記［１］〜［７］のいずれか１項に記載の素子。
［９］下記組成式（４）で表される金属錯体。

（式中、Ｌは上記式（３）で表される窒素原子含有環式化合物を表す。Ｌが複数ある場合、複数のＬはそれぞれ同一であっても異なっていてもよい。Ｘは対イオンを表す。Ｘが複数ある場合、複数のＸはそれぞれ同一であっても異なっていてもよい。Ｌ’は上記式（３）で表される窒素原子含有環式化合物以外の２座以下の配位子を表す。Ｌ’が複数ある場合、複数のＬ’はそれぞれ同一であっても異なっていてもよい。ａは０．５を超える数であり、ｂ及びｃは０以上の数である。ｂ及びｃはそれぞれ同一であっても異なっていてもよい。）
［１０］下記式（５）で表される窒素原子含有環式化合物。

（式中、Ａ¹¹、Ａ¹²、Ａ¹³及びＡ¹⁴は、置換基を有していてもよいヒドロカーボンジイル基を表す。Ａ¹¹、Ａ¹²、Ａ¹³及びＡ¹⁴はそれぞれ同一であっても異なっていてもよい。Ｒ²¹、Ｒ²²、Ｒ²³及びＲ²⁴は、水素原子又は置換基を有していてもよいヒドロカルビル基を表す。Ｒ²¹、Ｒ²²、Ｒ²³及びＲ²⁴はそれぞれ同一であっても異なっていてもよい。） [1] An element containing a metal complex of cerium and a nitrogen atom-containing cyclic compound represented by the following formula (1).

(In the formula, A ¹ represents a hydrocarbondiyl group which may have a substituent. A plurality of A ¹ may be the same or different from each other. N represents an integer of 3 or more. Z ¹ represents —O—, —S—, —NR ¹ —, or —PR ² —, but one or more is —NR ¹ —, and a plurality of Z ¹ may be the same or different. good .R ¹ and R ² be a hydrogen atom, or .R ¹ and R ² may .R ¹ also each be the same or different representing a hydrocarbyl group that may have a substituent If there are multiple, when a plurality of R ¹ is the optionally be the same or different .R ² there is a plurality, may be different even plurality of R ² are identical.)
[2] The element according to the above [1], wherein A ¹ , R ¹ or R ² has one or more nitrogen atom-containing heterocyclyl groups as substituents.
[3] The element according to [1] or [2], wherein the nitrogen atom-containing cyclic compound is represented by the following formula (2).

(Wherein, A ² and A ³ are a plurality good .A ² is also optionally substituted by one or each same .A ² and A ³ also represents an hydrocarbonoxy diyl group optionally having a substituent If, when the plurality of a ² there are a plurality of which may .A ³ optionally substituted by one or more identical respectively, may .Z ² be a plurality of a ³ are optionally substituted by one or more identical, -O- , -S -, - NR ¹ -, or -PR ² - If .Z ² there are a plurality representing a respective plurality of Z ² may optionally be the same or different .m represents an integer of 1 or more , p is an integer of 0 or more, m + p is case .R ¹⁰ is an integer of 3 or more which is more than one .R ¹⁰ representing a good hydro carbon diyl group which may have a substituent, a plurality of R ¹⁰ is L ¹⁰ may be the same or different from each other, and L ¹⁰ is a nitrogen atom-containing hetero optionally having a substituent. If .L ¹⁰ representing the cyclyl group is more, may be different even multiple L ¹⁰ are each identical.)
[4] The element according to [3], wherein m + p is an integer of 3 to 6 in the above formula (2).
[5] The element according to [3] or [4], wherein p is 0 in the formula (2).
[6] The element according to any one of [1] to [5], wherein the nitrogen atom-containing cyclic compound is represented by the following formula (3).

(In the formula, L ¹¹ , L ¹² , L ¹³ and L ¹⁴ represent a nitrogen atom-containing heterocyclyl group which may have a substituent. L ¹¹ , L ¹² , L ¹³ and L ¹⁴ are the same. may be different even .A ^11, a ^12, a ¹³ and a ¹⁴ are, .A representative of a good hydro carbon diyl group which may have a substituent group ^11, a ^12, a ¹³ and a ¹⁴ are each R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may represent a hydrocarbondiyl group which may have a substituent R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be the same or different.)
[7] The element according to [6], wherein the metal complex is a metal complex represented by the following composition formula (11).

(In the formula, L represents a nitrogen atom-containing cyclic compound represented by the above formula (3). When there are a plurality of L, the plurality of L may be the same or different. X is a counter ion. When there are a plurality of X, the plurality of X may be the same or different, and L ′ is a bidentate or lower arrangement other than the nitrogen atom-containing cyclic compound represented by the above formula (3). Represents a ligand, a ′ is a positive number, b ′ and c ′ are numbers greater than or equal to 0. b ′ and c ′ may be the same or different.
[8] The element according to any one of [1] to [7], wherein the element is an electroluminescent element.
[9] A metal complex represented by the following composition formula (4).

(In the formula, L represents a nitrogen atom-containing cyclic compound represented by the above formula (3). When there are a plurality of L, the plurality of L may be the same or different. X is a counter ion. When there are a plurality of X, the plurality of X may be the same or different, and L ′ is a bidentate or lower arrangement other than the nitrogen atom-containing cyclic compound represented by the above formula (3). In the case where there are a plurality of L ′, the plurality of L ′ may be the same or different from each other, a is a number exceeding 0.5, and b and c are a number of 0 or more. B and c may be the same or different.)
[10] A nitrogen atom-containing cyclic compound represented by the following formula (5).

(In the formula, A ¹¹ , A ¹² , A ¹³ and A ¹⁴ represent a hydrocarbondiyl group which may have a substituent. A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are the same, respectively. R ²¹ , R ²² , R ²³ and R ^{24 each} represents a hydrogen atom or a hydrocarbyl group which may have a substituent, wherein R ²¹ , R ²² , R ²³ and R ²⁴ are each They may be the same or different.)

  According to the present invention, it is possible to provide a cerium complex whose emission peak is located in the visible light region and sufficiently emits light in the visible light region, and to provide an element that sufficiently emits light in the visible light region using this complex. be able to.

  The present invention will be described below.

  In the present specification, “may have a substituent” means that the hydrogen atom constituting the compound or group described immediately after it is unsubstituted or a part or all of the hydrogen atoms are substituted. Includes both cases where it is substituted.

  In the present specification, “substituent” is used in the following meaning unless otherwise specified. Examples of the substituent bonded to the carbon atom include a hydrocarbyl group, a hydrocarbyloxy group, a hydrocarbylthio group, a heterocyclyl group, a halogen atom, a cyano group, an amide group, an imide group, a silyl group, an acyl group, an alkoxycarbonyl group, and an alkoxysulfonyl group. Group, alkoxyphosphoryl group, phosphino group, phosphine oxide group, amino group, hydroxyl group, mercapto group, carboxyl group, sulfo group, phosphoric acid group, phosphorous acid group, and nitro group; amino group, hydroxyl group, mercapto group, An anionic group obtained by removing a hydrogen atom from a group selected from the group consisting of a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphorous acid group is preferable, and preferably a hydrocarbyl group, a hydrocarbyloxy group, a hydrocarbylthio group, a heterocyclyl group Group, hydroxyl group, Carboxyl group, a sulfo group, or a phosphoric acid group, more preferably a hydrocarbyl group. Moreover, as a substituent couple | bonded with a nitrogen atom, a hydrocarbyl group is mentioned, for example. When a plurality of substituents are present, they may be the same or different.

  When the substituent is a group containing a carbon atom and not containing an aromatic ring, the number of carbon atoms of the substituent is usually 1 to 30, preferably 1 to 20, and more preferably. Is 1-10, more preferably 1-6, and particularly preferably 1-4.

  When the substituent is a group containing a carbon atom and an aromatic ring, the number of carbon atoms of the substituent is usually 2 to 30, preferably 3 to 20, and more preferably It is 4-10, More preferably, it is 4-6, Most preferably, it is 6.

  Examples of hydrocarbyl groups include methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, Decyl group, dodecyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group, norbornyl group, ammonium ethyl group, benzyl group, α , Α-dimethylbenzyl group, 1-phenethyl group, 2-phenethyl group, vinyl group, propenyl group, butenyl group, oleyl group, eicosapentaenyl group, docosahexaenyl group, 2,2-diphenylvinyl group, 1, 2,2-triphenylvinyl group, 2-phenyl-2-propenyl group, phenyl group, 2- Tolyl group, 4-tolyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-cyanophenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, terphenylyl group, 3,5- Diphenylphenyl group, 3,4-diphenylphenyl group, pentaphenylphenyl group, 4- (2,2-diphenylvinyl) phenyl group, 4- (1,2,2-triphenylvinyl) phenyl group, fluorenyl group, 1 -Naphthyl group, 2-naphthyl group, 9-anthryl group, 2-anthryl group, 9-phenanthryl group, 1-pyrenyl group, chrycenyl group, naphthacenyl group, and coronyl group, preferably methyl group, ethyl group 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, isobutyl group, tert-butyl group, Nethyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, 3,7-dimethyloctyl, benzyl, α, α-dimethylbenzyl, 1-phenethyl, 2-phenethyl, vinyl Group, propenyl group, butenyl group, phenyl group, 2-tolyl group, 4-tolyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, A terphenylyl group, a fluorenyl group, a 1-naphthyl group, or a 2-naphthyl group, more preferably a methyl group, an ethyl group, a tert-butyl group, a 1-propyl group, a 1-butyl group, a 2-butyl group, and an isobutyl group. Group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, 2-ethylhexyl group, Benzyl group, α, α-dimethylbenzyl group, vinyl group, butenyl group, phenyl group, 2-tolyl group, or 4-tolyl group, more preferably methyl group, ethyl group, 1-propyl group, hexyl group Or a vinyl group, particularly preferably a methyl group, an ethyl group, or a vinyl group.

  Examples of the hydrocarbyloxy group include methoxy group, ethoxy group, 1-propyloxy group, 2-propyloxy group, 1-butyloxy group, 2-butyloxy group, isobutyloxy group, tert-butyloxy group, pentyloxy group, hexyl. Oxy group, octyloxy group, decyloxy group, dodecyloxy group, 2-ethylhexyloxy group, 3,7-dimethyloctyloxy group, cyclopropyloxy group, cyclopentyloxy group, cyclohexyloxy group, 1-adamantyloxy group, 2- Adamantyloxy group, norbornyloxy group, ammonium ethoxy group, trifluoromethoxy group, benzyloxy group, α, α-dimethylbenzyloxy group, 2-phenethyloxy group, 1-phenethyloxy group, phenoxy group, methoxyphenoxy Group, octylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, and pentafluorophenyloxy group, preferably methoxy group, ethoxy group, 1-propyloxy group, 2-propyloxy group, 1 -Butyloxy group, 2-butyloxy group, isobutyloxy group, tert-butyloxy group, pentyloxy group, hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, 2-ethylhexyloxy group, or 3,7-dimethyloctyl An oxy group, more preferably a methoxy group, an ethoxy group, or a 1-propyloxy group.

  Examples of the hydrocarbylthio group include methylthio group, ethylthio group, 1-propylthio group, 2-propylthio group, 1-butylthio group, 2-butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, hexylthio group, octylthio group. Group, decylthio group, dodecylthio group, 2-ethylhexylthio group, 3,7-dimethyloctylthio group, cyclopropylthio group, cyclopentylthio group, cyclohexylthio group, 1-adamantylthio group, 2-adamantylthio group, norbornylthio group , Ammonium ethylthio group, trifluoromethylthio group, benzylthio group, α, α-dimethylbenzylthio group, 2-phenethylthio group, 1-phenethylthio group, phenylthio group, methoxyphenylthio group, octylphenylthio group, 1- Na A thiolthio group, a 2-naphthylthio group, and a pentafluorophenylthio group, preferably a methylthio group, an ethylthio group, a 1-propylthio group, a 2-propylthio group, a 1-butylthio group, a 2-butylthio group, and an isobutylthio group. , A pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, a 2-ethylhexylthio group, or a 3,7-dimethyloctylthio group, more preferably a methylthio group, an ethylthio group, or a 1-propylthio group. is there.

  Heterocyclyl groups include those containing one or more heteroatoms such as nitrogen, oxygen and sulfur atoms, such as piperidinyl, piperazinyl, benzofuryl, furyl, benzothienyl, thienyl, benzopyrrolyl. Group, pyrrolyl group, benzoimidazolyl group, imidazolyl group, benzopyrazolyl group, pyrazolyl group, benzoxazolyl group, oxazolyl group, benzothiazolyl group, thiazolyl group, quinolyl group, and pyridyl group, preferably benzofuryl group, furyl Group, benzothienyl group, thienyl group, benzopyrrolyl group, pyrrolyl group, benzimidazolyl group, imidazolyl group, benzopyrazolyl group, pyrazolyl group, benzoxazolyl group, oxazolyl group, benzothiazolyl group, thiazolyl group, quinolyl group, or A pyridyl group, more preferably a benzoimidazolyl group, an imidazolyl group, a benzopyrazolyl group, a pyrazolyl group, a benzoxazolyl group, an oxazolyl group, a benzothiazolyl group, a thiazolyl group, a quinolyl group, or a pyridyl group, and more preferably, A benzoimidazolyl group, an imidazolyl group, a pyrazolyl group, or a pyridyl group;

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably they are a fluorine atom or a chlorine atom.

  Examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, Examples thereof include a ditrifluoroacetamide group and a dipentafluorobenzamide group, preferably a formamide group, an acetamido group, a propioamide group, a butyroamide group, or a benzamide group.

An imide group is a group obtained by removing a hydrogen atom bonded to the nitrogen atom from an imide.
Examples of such an imide group include an N-succinimide group, an N-phthalimide group, and a benzophenone imide group, and an N-phthalimide group is preferable.

  The silyl group is a silyl group that may have 1 to 3 substituents selected from the group consisting of an alkyl group, an aryl group, and an arylalkyl group. Such silyl groups are preferably trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, dimethyl-i-propylsilyl, diethyl-i-propylsilyl, tert-butyldimethylsilyl. Group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group , Lauryldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, diphenylmethylsilyl group, tert-butyldiphenylsilyl group, or dimethylphenylsilyl group, more preferably Trimethylsilyl group, triethylsilyl group, or a tri-propyl silyl group, more preferably a trimethylsilyl group.

  Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group, and pentafluorobenzoyl group, preferably acetyl group or benzoyl group It is a group.

  Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl. Group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, and dodecyloxycarbonyl group Preferably, methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butoxy A carbonyl group, or isobutoxycarbonyl groups, more preferably a methoxycarbonyl group, or ethoxycarbonyl group.

  Examples of the alkoxysulfonyl group include methoxysulfonyl group, ethoxysulfonyl group, propyloxysulfonyl group, isopropyloxysulfonyl group, butoxysulfonyl group, isobutoxysulfonyl group, sec-butoxysulfonyl group, tert-butoxysulfonyl group, pentyl. Oxysulfonyl group, hexyloxysulfonyl group, heptyloxysulfonyl group, octyloxysulfonyl group, 2-ethylhexyloxysulfonyl group, nonyloxysulfonyl group, decyloxysulfonyl group, 3,7-dimethyloctyloxysulfonyl group, and dodecyloxysulfonyl Group, preferably methoxysulfonyl group, ethoxysulfonyl group, propyloxysulfonyl group, isopropyloxysulfonyl group, butto A Shisuruhoniru group, or isobutoxy sulfonyl group, more preferably a methoxy sulfonyl group, or an ethoxy sulfonyl group.

  Examples of the alkoxyphosphoryl group include a dimethoxyphosphoryl group, a diethoxyphosphoryl group, a dipropoxyphosphoryl group, a diisopropoxyphosphoryl group, a dibutoxyphosphoryl group, and an ethylenedioxyphosphoryl group, preferably a dimethoxyphosphoryl group. is there.

  The phosphino group is a phosphino group which may have one or two substituents selected from the group consisting of an alkyl group, an aryl group and an arylalkyl group. Examples of such phosphino groups include phenylphosphino groups, diphenylphosphino groups, methylphosphino groups, dimethylphosphino groups, ethylphosphino groups, diethylphosphino groups, propylphosphino groups, dipropylphosphino groups. , A butylphosphino group, and a dibutylphosphino group, preferably a diphenylphosphino group, a dimethylphosphino group, a diethylphosphino group, a dipropylphosphino group, or a dibutylphosphino group, more preferably , Diphenylphosphino group or dimethylphosphino group, particularly preferably diphenylphosphino group.

  The phosphine oxide group is a phosphine oxide group which may have one or two substituents selected from the group consisting of an alkyl group, an aryl group and an arylalkyl group. Examples of such phosphine oxide groups include phenylphosphine oxide groups, diphenylphosphine oxide groups, methylphosphine oxide groups, dimethylphosphine oxide groups, ethylphosphine oxide groups, diethylphosphine oxide groups, propylphosphine oxide groups, and dipropylphosphine oxide groups. Group, butylphosphine oxide group, and dibutylphosphine oxide group, preferably diphenylphosphine oxide group, dimethylphosphine oxide group, diethylphosphine oxide group, dipropylphosphine oxide group, or dibutylphosphine oxide group, more preferably Is a diphenylphosphine oxide group or a dimethylphosphine oxide group, particularly preferably diphenylphosphine oxide. It is.

The amino group is an amino group which may have 1 to 3 substituents selected from the group consisting of an alkyl group, an aryl group and an arylalkyl group, or —NH ₂ . Examples of such amino groups include phenylamino group, diphenylamino group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, butylamino group, and dibutylamino group. And preferably a diphenylamino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a dipropylamino group, or a dibutylamino group, more preferably a methylamino group, an ethylamino group, Or it is a diphenylamino group.

  An anionic group obtained by removing a hydrogen atom from an amino group, a hydroxyl group, a mercapto group, a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphorous acid group may have a counter ion. Examples of the counter ion include a lithium ion, a sodium ion, a potassium ion, a rubidium ion, a cesium ion, and an ammonium ion, and preferably a sodium ion, a potassium ion, or an ammonium ion.

1. Element of the Present Invention <1.1 Metal Complex Used for Element of Present Invention>
In one embodiment, the nitrogen atom-containing cyclic compound is represented by the following formula (1).

In the formula (1), A ¹ represents a hydrocarbondiyl group which may have a substituent. A plurality of A ¹ may be the same or different.

  Examples of the hydrocarbon diyl group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a methylethylene group, a methylpropylene group, an ethylethylene group, an ethylpropylene group, and a methylbutylene group. , Ethylhexylene group, dimethyloctylene group, cyclopropylene group, cyclopentylene group, cyclohexylene group, adamantanediyl group, norbornanediyl group, phenylenemethylene group, vinylene group, propenylene group, butenylene group, diphenylvinylene group, phenyl Vinylene group, phenylpropenylene group, phenylene group, methylphenylene group, trifluoromethylphenylene group, cyanophenylene group, biphenyldiyl group, terphenyldiyl group, tetraphenylphenylene group, (2,2 Diphenylvinyl) phenylene group, (1,2,2-triphenylvinyl) phenylene group, fluorenediyl group, naphthylene group, anthrylene group, phenanthrylene group, and pyrenediyl group, preferably methylene group, ethylene group, Propylene group, butylene group, methylethylene group, methylpropylene group, ethylethylene group, ethylpropylene group, methylbutylene group, ethylhexylene group, phenylenemethylene group, vinylene group, propenylene group, or phenylene group, more preferably , Methylene group, ethylene group, propylene group, butylene group, methylethylene group, methylpropylene group, vinylene group, or propenylene group, more preferably methylene group, ethylene group, propylene group, butylene group, methylethylene group, Or A propylene group, particularly preferably a methylene group, an ethylene group, or propylene group.

  n represents an integer greater than or equal to 3, Preferably it is an integer of 3-10, More preferably, it is an integer of 3-6, More preferably, it is 4.

Z ¹ represents —O—, —S—, —NR ¹ —, or —PR ² —. One or more of the plurality of Z ¹ are —NR ¹ —. A plurality of Z ¹ may be the same or different, but preferably all Z ¹ are —NR ¹ —.

R ¹ represents a hydrogen atom or a hydrocarbyl group which may have a substituent. Examples of hydrocarbyl groups include methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, Decyl group, dodecyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group, norbornyl group, ammonium ethyl group, benzyl group, α , Α-dimethylbenzyl group, 1-phenethyl group, 2-phenethyl group, vinyl group, propenyl group, butenyl group, oleyl group, eicosapentaenyl group, docosahexaenyl group, 2,2-diphenylvinyl group, 1, 2,2-triphenylvinyl group, 2-phenyl-2-propenyl group, phenyl group, 2- Tolyl group, 4-tolyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-cyanophenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, terphenylyl group, 3,5- Diphenylphenyl group, 3,4-diphenylphenyl group, pentaphenylphenyl group, 4- (2,2-diphenylvinyl) phenyl group, 4- (1,2,2-triphenylvinyl) phenyl group, fluorenyl group, 1 -Naphthyl group, 2-naphthyl group, 9-anthryl group, 2-anthryl group, 9-phenanthryl group, 1-pyrenyl group, chrycenyl group, naphthacenyl group, and coronyl group, preferably methyl group, ethyl group 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, isobutyl group, tert-butyl group, Nethyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, 3,7-dimethyloctyl, benzyl, α, α-dimethylbenzyl, 1-phenethyl, 2-phenethyl, vinyl Group, propenyl group, butenyl group, phenyl group, 2-tolyl group, 4-tolyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, A terphenylyl group, a fluorenyl group, a 1-naphthyl group, or a 2-naphthyl group, more preferably a methyl group, an ethyl group, a tert-butyl group, a 1-propyl group, a 1-butyl group, a 2-butyl group, and an isobutyl group. Group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, 2-ethylhexyl group, Benzyl group, α, α-dimethylbenzyl group, vinyl group, butenyl group, phenyl group, 2-tolyl group, or 4-tolyl group, more preferably methyl group, ethyl group, 1-propyl group, hexyl group Or a vinyl group, particularly preferably a methyl group, an ethyl group, or a 1-propyl group.

R ² represents a hydrogen atom or a hydrocarbyl group which may have a substituent. Examples of hydrocarbyl groups include methyl, ethyl, benzyl, 1-phenethyl, 2-phenethyl, vinyl, propenyl, butenyl, phenyl, 2-tolyl, 4-tolyl, 2- Biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, terphenylyl group, 3,5-diphenylphenyl group, 3,4-diphenylphenyl group, pentaphenylphenyl group, 4- (2,2-diphenylvinyl) phenyl group, 4- (1,2,2-triphenylvinyl) phenyl group, fluorenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2 -Phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 6-chrenyl group, 1-benzo [c] phenanthryl group, 2-benzo [c] phenanthryl group, 3- Benzo [c] phenanthryl, 4-benzo [c] phenanthryl, 5-benzo [c] phenanthryl, 6-benzo [c] phenanthryl, 1-benzo [g] chrysenyl, 2-benzo [g] chrysenyl Group, 3-benzo [g] chrysenyl group, 4-benzo [g] chrysenyl group, 5-benzo [g] chrysenyl group, 6-benzo [g] chrysenyl group, 7-benzo [g] chrysenyl group, 8-benzo [G] Chrysenyl group, 9-benzo [g] chrysenyl group, 10-benzo [g] chrysenyl group, 11-benzo [g] chrysenyl group, 12-benzo [g] group Examples include senyl group, 13-benzo [g] chrysenyl group, 14-benzo [g] chrysenyl group, benzofluorenyl group, and dibenzofluorenyl group, preferably phenyl group, 2-tolyl group, 4-tolyl. Group, fluorenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, or 4-pyrenyl group, more preferably phenyl group, 2-tolyl group, 4 -Tolyl group, fluorenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, or 9-ant A tolyl group, more preferably a phenyl group, a 2-tolyl group, or a 4-tolyl group, and particularly preferably a phenyl group.

R ¹ and R ² may be the same or different. When R ¹ are a plurality, it may be different even plurality of R ¹ are the same. When R ² are a plurality, it may be different even plurality of R ² are identical.

Suitable forms of nitrogen atom-containing cyclic compounds, A ^1, R ¹ or R ² in the formula (1) is, as a substituent, include embodiments having one or more nitrogen-containing heterocyclyl group. The nitrogen atom-containing heterocyclyl group means a heterocyclyl group containing one or more nitrogen atoms as a hetero atom. The nitrogen atom-containing heterocyclyl group may have a heteroatom other than a nitrogen atom as long as it has one or more nitrogen atoms. Specific examples and preferred examples of the nitrogen atom-containing heterocyclyl group are the same as those of the specific examples and preferred examples of those containing a nitrogen atom among the heterocyclyl groups described above as examples of the containing substituent. The nitrogen atom-containing heterocyclyl group is preferably a group represented by the following formulas (6) to (10), more preferably a group represented by the following formula (8) or (10).

式（６）において、Ｒ³は水素原子又は置換基を有していてもよいヒドロカルビル基を表し、ヒドロカルビル基の具体的な例及び好ましい例は、上記Ｒ¹における説明と同様である。Ｒ⁴は、置換基を表し、ｅは０〜２の整数である。Ｒ³が結合する窒素原子とＲ⁴が結合する炭素原子とが互いに隣接位にある場合、Ｒ³及びＲ⁴は、結合して環を形成していてもよい。ｅが２であり、２つのＲ⁴が互いに隣接する炭素原子にそれぞれ結合している場合、２つのＲ⁴は結合して環を形成していてもよい。ｅが２である場合、２つのＲ⁴はそれぞれ同一であっても異なっていてもよい。

In the formula (6), R ³ represents a hydrogen atom or a hydrocarbyl group which may have a substituent, and specific examples and preferred examples of the hydrocarbyl group are the same as those described for R ¹ above. R ⁴ represents a substituent, and e is an integer of 0 to 2. If the carbon atom to which the nitrogen atom and R ⁴ wherein R ³ is attached is bound is in the adjacent position to one another, R ³ and R ⁴ may combine to form a ring. When e is 2 and two R ⁴ are bonded to adjacent carbon atoms, the two R ⁴ may be bonded to form a ring. When e is 2, two R ^{4 s} may be the same or different.

式（７）において、Ｒ⁵は、置換基を表し、ｆは０〜３の整数である。ｆが２以上の整数であり、複数のＲ⁵が互いに隣接する炭素原子にそれぞれ結合している場合、複数のＲ⁵は結合して環を形成していてもよい。ｆが２以上の整数である場合、複数のＲ⁵はそれぞれ同一であっても異なっていてもよい。

In Formula (7), R ⁵ represents a substituent, and f is an integer of 0 to 3. When f is an integer of 2 or more and a plurality of R ⁵ are bonded to carbon atoms adjacent to each other, the plurality of R ⁵ may be bonded to form a ring. When f is an integer greater than or equal to 2, several R < ⁵ > may be same or different, respectively.

式（８）において、Ｘ¹は、酸素原子、硫黄原子、又は−ＮＲ⁶−であり、好ましくは−ＮＲ⁶−である。Ｒ⁶は水素原子又は置換基を有していてもよいヒドロカルビル基を表し、ヒドロカルビル基の具体的な例及び好ましい例は、上記Ｒ¹における説明と同様である。

In the formula (8), X ¹ is an oxygen atom, a sulfur atom, or —NR ⁶ —, preferably —NR ⁶ —. R ⁶ represents a hydrogen atom or a hydrocarbyl group which may have a substituent, and specific examples and preferred examples of the hydrocarbyl group are the same as those described for R ¹ above.

R ⁷ represents a substituent, and g is an integer of 0 to 2. If the carbon atom to which the nitrogen atom and R ⁷ which R ⁶ is attached is bound is in the adjacent position to each other, R ⁶ and R ⁷ may combine to form a ring. g is 2, when two R ⁷ are attached respectively to the carbon atoms adjacent to each other, the two R ⁷ may form a ring. When g is 2, two R ^{7 s} may be the same or different.

式（９）において、Ｒ⁸は、置換基を表し、ｈは０〜３の整数である。ｈが２以上の整数であり、複数のＲ⁸が互いに隣接する炭素原子にそれぞれ結合している場合、複数のＲ⁸は結合して環を形成していてもよい。ｈが２以上の整数である場合、複数のＲ⁸はそれぞれ同一であっても異なっていてもよい。

In Formula (9), R ⁸ represents a substituent, and h is an integer of 0 to 3. When h is an integer of 2 or more and a plurality of R ⁸ are bonded to adjacent carbon atoms, the plurality of R ⁸ may be bonded to form a ring. When h is an integer of 2 or more, the plurality of R ⁸ may be the same or different.

式（１０）において、Ｒ⁹は、置換基を表し、ｉは０〜４の整数である。ｉが２以上の整数であり、複数のＲ⁹が互いに隣接する炭素原子にそれぞれ結合している場合、複数のＲ⁹は結合して環を形成していてもよい。

In Formula (10), R ⁹ represents a substituent, and i is an integer of 0 to 4. When i is an integer of 2 or more and a plurality of R ⁹ are bonded to adjacent carbon atoms, the plurality of R ⁹ may be bonded to form a ring.

The nitrogen atom-containing cyclic compound that can be suitably applied in the present invention is represented by the structure of the following formula (2).

A ² and A ³ represent a hydrocarbondiyl group which may have a substituent. Specific examples and preferred examples of the hydrocarbondiyl group are the same as those described above for A ¹ . A ² and A ³ may be the same or different. If A ² there are a plurality, it may be a plurality of A ² is not be the same or different. If A ³ there are a plurality, it may be a plurality of A ³ are optionally substituted by one or more identical.

Z ² represents —O—, —S—, —NR ¹ — or —PR ¹ —, preferably —NR ¹ —. Specific examples and preferred examples of R ¹ are as described above. If Z ² there are a plurality, may be a plurality of Z ² may have be the same or different.

  m represents an integer greater than or equal to 1, Preferably it is an integer of 2-10, More preferably, it is an integer of 2-6, More preferably, it is 4.

  p represents an integer of 0 or more. m + p is an integer greater than or equal to 3, Preferably it is an integer of 3-10, More preferably, it is an integer of 3-6, More preferably, it is 4.

R ¹⁰ represents a hydrocarbondiyl group which may have a substituent. Examples of the hydrocarbon diyl group include a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, octamethylene group, decamethylene group, dodecamethylene group, cyclopropylene group, cyclopentylene group, cyclohexylene group, Adamantanediyl group, norbornanediyl group, phenylenemethylene group, vinylene group, propenylene group, butenylene group, diphenylvinylene group, phenylvinylene group, phenylpropenylene group, phenylene group, biphenyldiyl group, terphenyldiyl group, tetraphenylphenylene group , Fluorenediyl group, naphthylene group, anthrylene group, phenanthrylene group, and pyrenediyl group, preferably methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethyl group. Group, cyclohexylene group, phenylenemethylene group, vinylene group, propenylene group, butenylene group, phenylvinylene group, phenylpropenylene group or phenylene group, more preferably methylene group, ethylene group, trimethylene group, tetramethylene group. Group, a cyclohexylene group, a phenyl vinylene group, or a phenylene group, more preferably a methylene group, an ethylene group, or a trimethylene group, and particularly preferably a methylene group. If there are a plurality of R ¹⁰ s may be different even multiple R ¹⁰ are each identical.

L ¹⁰ represents a nitrogen atom-containing heterocyclyl group. As the nitrogen atom-containing heterocyclyl group, groups represented by the above formulas (6) to (10) are preferable. If L ¹⁰ there are a plurality, may be a plurality of L ¹⁰ may have be the same or different.

A more preferred form of the nitrogen atom-containing cyclic compound used in the present invention is represented by the structure of the following formula (3).

L ¹¹ , L ¹² , L ¹³ and L ¹⁴ represent a nitrogen atom-containing heterocyclyl group which may have a substituent, preferably a group represented by the above formulas (6) to (10), or hydrogen An atom, more preferably a group represented by the above formulas (8) to (10). L ¹¹ , L ¹² , L ¹³ and L ¹⁴ may be the same or different.

A ¹¹ , A ¹² , A ¹³ and A ¹⁴ represent a hydrocarbondiyl group which may have a substituent. Specific examples and preferred examples of the hydrocarbondiyl group are the same as those described above for A ¹ . A ¹¹ , A ¹² , A ¹³ and A ¹⁴ may be the same or different.

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ represent a hydrocarbondiyl group which may have a substituent. Specific examples and preferred examples of the hydrocarbondiyl group are the same as those described above for R ¹⁰ . R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be the same or different.

Another form of the nitrogen atom-containing cyclic compound that can be more suitably applied in the present invention is represented by the structure of the following formula (5).

A ¹¹ , A ¹² , A ¹³ and A ¹⁴ represent a hydrocarbondiyl group which may have a substituent. A ¹¹ , A ¹² , A ¹³ and A ¹⁴ may be the same or different.

R ²¹ , R ²² , R ²³ and R ²⁴ represent a hydrogen atom or a hydrocarbyl group which may have a substituent. R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different. Specific examples and preferred examples of the hydrocarbyl group for R ²¹ , R ²² , R ²³ and R ²⁴ are the same as those described above for R ¹ .

Examples of the nitrogen atom-containing cyclic compound include ligands represented by the following formulas (A-1) to (A-18), and among these, the following formula (A-5) to A ligand represented by (A-15), more preferably a ligand represented by the following formulas (A-7) to (A-14), and still more preferably a ligand represented by the following formula (A-9). ) To (A-13).

  The metal complex used in the device of the present invention is a metal complex of cerium and the nitrogen atom-containing cyclic compound. In addition, the said nitrogen atom containing cyclic compound may be only 1 type, or may mix 2 or more types in 1 molecule.

  In addition to the nitrogen atom-containing cyclic compound, the metal complex used in the device of the present invention contains a bidentate or lower (monodentate or bidentate) ligand (L ′) and / or counter ion (X). One or a plurality of them may be contained. The ligand (L ′) may be any ligand other than the nitrogen atom-containing cyclic compound.

  The ligand (L ′) is preferably an atomic group containing an atom selected from the group consisting of an oxygen atom, a nitrogen atom and a phosphorus atom, such as water, methanol, ethanol, acetone, tetrahydrofuran, dimethyl sulfoxide, triarylphosphine. Oxide, trialkylphosphine oxide, pyridine, quinoline, pyrazole, imidazole, oxazole, thiazole, benzimidazole, benzoxazole, benzothiazole, triazine, pyrimidine, pyrazine, bipyridine, biquinoline, phenanthroline, triarylphosphine, trialkylphosphine, and tri An alkylamine is mentioned. The ligand (L ′) may be one of these, or two or more may be mixed in one molecule.

  Examples of the counter ion (X) include fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, acetate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate. Ion, hexafluoroantimony ion, hexafluoroarsenic ion, methanesulfonic acid ion, trifluoromethanesulfonic acid ion, trifluoroacetic acid ion, benzenesulfonic acid ion, paratoluenesulfonic acid ion, dodecylbenzenesulfonic acid ion, tetraphenylborate ion, Examples thereof include an ion such as tetrakis (pentafluorophenyl) borate ion; and a polymer compound containing a repeating unit having any ion selected from these ions. The ligand (L ′) may be negatively charged, and in this case, the counter ion (X) may be a cation. Examples of the cation include lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, and ammonium ion. The counter ion (X) is preferably fluoride ion, chloride ion, nitrate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimony ion, hexafluoroarsenic ion, methanesulfonic acid. Ion, trifluoromethanesulfonate ion, trifluoroacetate ion, benzenesulfonate ion, p-toluenesulfonate ion, dodecylbenzenesulfonate ion, tetraphenylborate ion, or tetrakis (pentafluorophenyl) borate ion, more preferably , Chloride ion, nitrate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, methanesulfonate ion, trifluoromethanesulfonate ion, Fluoroacetate ion, benzenesulfonate ion, p-toluenesulfonate ion, tetraphenylborate ion, or tetrakis (pentafluorophenyl) borate ion, more preferably perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion , Trifluoromethanesulfonate ion, trifluoroacetate ion, or tetraphenylborate ion, particularly preferably tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonate ion, or tetraphenylborate ion. The counter ion (X) is one of these, or two or more may be mixed in one molecule.

Specifically, the metal complex used in the device of the present invention may be composed of a composition represented by the following composition formula (11).

  In the formula (11), L represents the nitrogen atom-containing cyclic compound, preferably a nitrogen atom-containing cyclic compound represented by the formula (3). X represents a counter ion. L ′ represents a bidentate or lower ligand other than the compound represented by L, preferably a bidentate or lower ligand other than the nitrogen atom-containing cyclic compound represented by the formula (3). . Specific examples and preferred examples of L ′ and X are the same as described above. Among them, L is a nitrogen atom-containing cyclic compound represented by the above formula (3), and L ′ is a bidentate or lower ligand other than the nitrogen atom-containing cyclic compound represented by the above formula (3). Preferably there is.

  In the formula (11), a ′, b ′ and c ′ are determined by the number of coordination atoms of the ligand and the charging ratio at the time of synthesis. a ′ is a positive number, preferably a number exceeding 0.5, more preferably a number satisfying 0.5 <a ′ <1.5, and further preferably 0.7 <a ′ <1. .2 and particularly preferably 0.9 <a ′ <1.1. b ′ is a number of 0 or more, preferably a number satisfying 0 ≦ b ′ ≦ 4, and more preferably a number satisfying 0 ≦ b ′ ≦ 3. c ′ is a number of 0 or more, preferably a number satisfying 0 ≦ c ′ ≦ 6, more preferably a number satisfying 0 ≦ c ′ ≦ 3, and further preferably 0 ≦ c ′ ≦ 2. The number to be satisfied, particularly preferably 0.

Specific examples of the metal complex used in the device of the present invention include metal complexes composed of compositions represented by the following formulas (B-1) to (B-6).

<1.2 Manufacturing Method of Metal Complex Used for Device of the Present Invention>
The metal complex used in the device of the present invention includes, for example, a nitrogen atom-containing cyclic compound and a metal salt (for example, cerium (III) chloride or cerium (III) trifluoromethanesulfonate), a solvent (for example, methanol or acetonitrile). ) At room temperature and the resulting precipitate is recovered or the solvent of the resulting solution is distilled off.

  When the above-mentioned mixing is performed, a solvent (example) is used to uniformly dissolve the metal salt and the nitrogen atom-containing cyclic compound in the solvent, or to facilitate stirring when the solution has a high viscosity. : An aqueous solvent such as a buffer solution or an organic solvent) may be used, and an organic solvent is preferably used.

  Examples of the organic solvent include nitrile solvents such as acetonitrile and benzonitrile; chlorine solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, and o-dichlorobenzene; Ether solvents such as dioxane; aromatic hydrocarbon solvents such as toluene and xylene; cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, etc. Aliphatic hydrocarbon solvents; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl Ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and other polyhydric alcohols and derivatives thereof; methanol, ethanol, propanol, isopropanol, cyclo Examples thereof include alcohol solvents such as hexanol; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents may be used alone or in combination of two or more.

<1.3 Device of the Present Invention>
The element of the present invention contains a metal complex of cerium and the above nitrogen atom-containing cyclic compound.

  As an element of the present invention, for example, in an element having one or a plurality of layers containing an organic compound sandwiched between a pair of electrodes composed of an anode and a cathode and the pair of electrodes, the above organic compound is used. Examples include an element in which at least one of the layers including the metal complex contains the metal complex.

  The element of the present invention may be either a light emitting element or a photoelectric conversion element. The case where the element of the present invention is a light emitting element will be described first, and then the case where it is a photoelectric conversion element will be described.

<1.3.1 Light Emitting Element>
A light emitting element usually includes a layer having a function of emitting light, that is, a light emitting layer, between electrodes composed of an anode and a cathode. Moreover, in order to improve luminous efficiency and durability, one or more known layers having functions other than the function of emitting light may be included. Examples of such a layer include a charge transport layer, a charge blocking layer, a charge injection layer, and a buffer layer. When the element of the present invention is a light emitting element, each of the light emitting layer, the charge transport layer, the charge blocking layer, the charge injection layer, the buffer layer, and the like may be composed of one layer or two or more layers. . The metal complex is preferably contained in one or more of the above layers, and is preferably contained in the light emitting layer.

  The light emitting layer is a layer having a function of emitting light. The hole transport layer is a layer having a function of transporting holes. The electron transport layer is a layer having a function of transporting electrons. These electron transport layer and hole transport layer are collectively referred to as a charge transport layer. The charge blocking layer is a layer having a function of confining holes or electrons in the light emitting layer. Of the charge blocking layer, a layer that transports electrons and confines holes is referred to as a hole blocking layer, and a layer that transports holes and confines electrons is referred to as an electron blocking layer.

  Examples of the buffer layer include a layer containing a conductive polymer compound adjacent to the anode.

When the element of the present invention is a light emitting element, examples of the structure of the light emitting element include the following structures a) to q).
a) anode / light emitting layer / cathode b) anode / hole transport layer / light emitting layer / cathode c) anode / light emitting layer / electron transport layer / cathode d) anode / light emitting layer / hole blocking layer / cathode e) anode / Hole transport layer / light emitting layer / electron transport layer / cathode f) anode / charge injection layer / light emitting layer / cathode g) anode / light emitting layer / charge injection layer / cathode h) anode / charge injection layer / light emitting layer / charge injection Layer / cathode i) anode / charge injection layer / hole transport layer / light emitting layer / cathode j) anode / hole transport layer / light emitting layer / charge injection layer / cathode k) anode / charge injection layer / hole transport layer / Light emitting layer / charge injection layer / cathode l) anode / charge injection layer / light emitting layer / electron transport layer / cathode m) anode / light emitting layer / electron transport layer / charge injection layer / cathode n) anode / charge injection layer / light emitting layer / Electron transport layer / charge injection layer / cathode o) anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / cathode p) anode / hole transport layer / emission Layer / electron transport layer / charge injection layer / cathode q) anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode (where “/” indicates that each layer is adjacent to each other) Note that two or more light emitting layers, hole transport layers, and electron transport layers may be used independently.)

  Of the charge transport layers provided adjacent to the electrodes, those having the function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are generally charge injection layers (ie, hole injection layers). And an electron injection layer). Examples of the element provided with the charge injection layer include an element provided with the charge injection layer adjacent to the cathode and an element provided with the charge injection layer adjacent to the anode.

  In the element of the present invention, an insulating layer may be provided adjacent to the electrode in order to improve adhesion with the electrode or to improve charge injection from the electrode. Examples of the material used for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. The thickness of the insulating layer is usually 2 nm or less. As an element provided with an insulating layer, the element provided with the said insulating layer adjacent to a cathode and the element provided with the said insulating layer adjacent to an anode are mentioned, for example.

  When the element of the present invention is a light emitting element, the light emitting layer can inject holes from the adjacent layer on the anode side when an electric field is applied, and can inject electrons from the adjacent layer on the cathode side, It has a function of moving injected charges (that is, electrons and holes) by the force of an electric field, a field of recombination of electrons and holes, and a function of connecting this to light emission. The light emitting layer of the element of the present invention preferably contains the above metal complex, and may contain a host material using this metal complex as a guest material.

  Examples of the host material include a compound having a fluorene skeleton, a compound having a carbazole skeleton, a compound having a diarylamine skeleton, a compound having a pyridine skeleton, a compound having a pyrazine skeleton, a compound having a triazine skeleton, and a compound having an arylsilane skeleton Is mentioned. The T1 of the host material (energy level in the lowest triplet excited state) is preferably larger than T1 of the guest material, and more preferably the difference is larger than 0.2 eV. Moreover, in order to improve the uniformity and mechanical properties of the layer, a polymer compound having no charge transporting property may be contained. Examples of the polymer compound that does not have charge transportability include non-conjugated polymer compounds, and those that do not extremely inhibit charge transportability and those that do not strongly absorb visible light are preferable. Examples of the non-conjugated polymer compound include polystyrenes (polystyrene, isotactic polystyrene, poly (α-methylstyrene), etc.), polyethylenes (HD polyethylene, etc.), polypropylene, polyisoprene, polybutadiene, poly (4- Methyl-1-pentene), poly (tetrafluoroethylene), polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, poly (2-hydroxyethyl methacrylate), and polyvinyl chloride; selected from these non-conjugated polymer compounds And copolymers having a repeating unit constituting the compound (random copolymer, block copolymer, etc.). The host material may be a low molecular compound or a high molecular compound. In addition, a light-emitting layer in which a light-emitting material is doped into the host material can be formed by applying a mixture of a host material and a light-emitting material such as a metal complex or by co-evaporation.

  Content of the said metal complex in the layer containing the metal complex in an element is 0.01-100 weight% normally with respect to the said whole layer, 0.1-50 weight% is preferable, 1-50 weight % Is more preferable.

  Examples of the material used for the hole transport layer include, for example, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2. Examples thereof include compounds described in literatures such as -209988, JP-A-3-37992, and JP-A-3-152184. Specifically, for example, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine compound group in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, Polyaniline and derivatives thereof, polyaminophen and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, and poly (2,5-thienylene vinylene) and derivatives thereof.

  The thickness of the hole transport layer is set so that the light emission efficiency or photoelectric efficiency and the drive voltage have appropriate values, and the optimum value varies depending on the material used, but a thickness that does not cause pinholes is required. When the hole transport layer is too thick, the driving voltage of the device tends to increase. Therefore, the thickness of the hole transport layer is preferably 1 nm to 1 μm, more preferably 2 nm to 500 nm, and still more preferably 5 nm to 200 nm.

  Examples of materials used for the electron transport layer include, for example, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2-209998. And compounds described in documents such as JP-A-3-379992 and JP-A-3-152184. Specifically, for example, oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyano Examples include ethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, and polyfluorene and its derivatives.

  The thickness of the electron transport layer is set so that the light emission efficiency or photoelectric efficiency and the drive voltage have appropriate values, and the optimum value varies depending on the material used, but a thickness that does not cause pinholes is required. An electron transport layer that is too thick tends to increase the driving voltage of the device. Therefore, the thickness of the electron transport layer is preferably 1 nm to 1 μm, more preferably 2 nm to 500 nm, and still more preferably 5 nm to 200 nm.

  Each layer is formed on an adjacent layer or substrate. Examples of the forming method include a vacuum deposition method (resistance heating deposition method, electron beam method, etc.), sputtering method, LB method, molecular lamination method, and coating method, and the coating method is preferable because the manufacturing process can be simplified. .

  Examples of the coating method include spin coating method, casting method, dip coating method, gravure coating method, bar coating method, roll coating method, spray coating method, screen printing method, flexographic printing method, offset printing method and inkjet method. Among these, the spin coating method, casting method, roll coating method, spray coating method, screen printing method, flexographic printing method, offset printing method or ink jet method are preferable, and the roll coating method, spray coating method or flexographic printing method is preferable. More preferred.

  The element of the present invention is usually formed using a substrate. An electrode is formed on one surface of the substrate, and each layer of the element is formed on the other surface. The substrate used in the present invention may be any substrate that does not chemically change when forming each layer of the electrode and element. For example, a substrate made of a material selected from the group consisting of glass, plastic, polymer film, and silicon is used. Can be mentioned. When this substrate is opaque, it is preferable to form a transparent or translucent electrode as the opposite electrode.

  Usually, the anode and / or the cathode contained in the element of the present invention is transparent or translucent, and the anode is preferably transparent or translucent.

  Examples of the material used for the anode include a conductive metal oxide film and a translucent metal thin film. Specifically, for example, indium oxide, zinc oxide, tin oxide, and composites thereof (indium tin oxide (ITO) and indium zinc oxide), antimony tin oxide, NESA, gold, platinum , Silver, and copper. Of these, ITO, indium / zinc / oxide, and tin oxide are preferable. Further, as the anode, an organic transparent conductive film (polyaniline and derivatives thereof, polyaminophen and derivatives thereof, or the like) may be used.

  Examples of the method for forming the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.

  The thickness of the anode can be set in consideration of light transmittance and electrical conductivity, and is preferably 10 nm to 10 μm, more preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm. Is more preferable.

  The material used for the cathode is preferably a material having a low work function, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium. Metals such as samarium, europium, terbium and ytterbium; alloys of two or more metals selected from the group consisting of those metals; one or more metals selected from the group consisting of those metals and gold, silver, platinum , Copper, manganese, titanium, cobalt, nickel, tungsten, and an alloy with one or more metals selected from the group consisting of tin; graphite; and graphite intercalation compounds. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

  Examples of the method for forming the cathode include a vacuum deposition method, a sputtering method, and a laminating method in which a metal thin film is thermocompression bonded. Further, a cathode having a laminated structure of two or more layers may be formed.

  The thickness of the cathode can be set in consideration of electric conductivity and / or durability, and is preferably 10 nm to 10 μm, more preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm. Further preferred. Further, a layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like having an average thickness of 2 nm or less may be provided between the cathode and the organic layer.

  In the element of the present invention, a protective layer and / or a protective cover for protecting the element may be formed after forming the cathode in order to protect the element from the outside and use it stably for a long time.

  Examples of the material used for such a protective layer include polymer compounds, metal oxides, metal fluorides, and metal borides. Examples of the protective cover include a glass plate and a plastic plate having a surface subjected to low water permeability treatment. Among these, it is preferable that the protective cover is bonded to the element using a thermosetting resin or a photocurable resin to seal the element.

  As the charge injection layer, for example, a layer containing a conductive polymer, a layer containing a material having an ionization potential of an intermediate value between the anode material and the hole transport material contained in the hole transport layer (anode and hole transport) And a layer containing a material having an electron affinity with an intermediate value between the cathode material and the electron transport material contained in the electron transport layer (provided between the cathode and the electron transport layer). Case).

  The material used for the charge injection layer may be selected according to the relationship between the material of the electrode and / or the material of the layer adjacent to the charge injection layer. Specifically, for example, polyaniline and derivatives thereof, polyaminophen and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, aromatic Examples thereof include conductive polymers such as polymers containing an amine structure in the main chain or side chain, metal phthalocyanines (such as copper phthalocyanine), and carbon.

  The thickness of the charge injection layer is preferably 1 nm to 100 nm, more preferably 1 nm to 50 nm, and even more preferably 1 nm to 10 nm.

  When the element of the present invention is a light emitting element, the light emitting element can be used for a planar light source, a segment display device, a dot matrix display device, a backlight of a liquid crystal display device, or illumination.

  In order to obtain planar light emission using the light emitting element, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain patterned light emission, a method of installing a mask having a patterned window on the surface of a planar light emitting element, a part of the organic layer is formed extremely thick and substantially non-light emitting There are a method of forming a part and a method of forming either one or both of an anode and a cathode in a pattern. A segment display device capable of displaying numbers, characters, simple symbols, etc. can be obtained by forming a pattern by any one of these methods and arranging several electrodes so that they can be turned ON / OFF independently. Further, a dot matrix display device can be obtained by forming both the anode and the cathode in a stripe shape so as to be orthogonal to each other.

  In this dot matrix display device, partial color display or multicolor display is possible by separately applying a plurality of types of light emitting materials having different light emission colors or using a color filter or a light emission conversion filter. Further, the dot matrix display device can be driven passively, and can be driven actively by combining with a TFT or the like. These display devices can be used in computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

  The planar light-emitting element is self-luminous thin and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. Further, by using a flexible substrate, it can be used as a curved light source or display device.

  When the element of the present invention is a switching element, the switching element can be used for a liquid crystal display device having an active matrix driving circuit.

<1.3.2 Photoelectric conversion element>
Next, the case where the element of the present invention is a photoelectric conversion element will be described below.

  The photoelectric conversion element usually has an anode, a cathode, and a charge separation layer. The charge separation layer is located between the anode and the cathode. The photoelectric conversion element may include an arbitrary component other than the charge separation layer between the anode and the cathode. The layer containing the metal complex may be included in the charge separation layer or may be included as the optional component.

  Specific examples and preferred examples of materials and shapes of the cathode and the anode are the same as those described in the light-emitting element. The anode and / or the cathode may be formed in a comb shape. In this case, the electrode may be opaque, but is preferably transparent or translucent.

  When the element of the present invention is a photoelectric conversion element, the charge separation layer of the photoelectric conversion element usually contains an electron donating compound and an electron accepting compound. Examples of the electron donating compound include a conjugated polymer compound, and examples of the conjugated polymer compound include a conjugated polymer compound containing a thiophenediyl group and a conjugated polymer compound containing a fluorenediyl group. . Moreover, as an electron-accepting compound, fullerene and a fullerene derivative are mentioned, for example.

  The photoelectric conversion element is usually formed on a substrate. Specific examples and preferred examples of the substrate are the same as those described for the substrate in the light-emitting element.

  When the element of this invention is a photoelectric conversion element, this photoelectric conversion element can be used for a solar cell.

式（４）中、Ｌは下記式（３）：

で表される窒素原子含有環式化合物を表す。 2. Novel Compound of the Present Invention The present invention provides a metal complex represented by the following composition formula (4).

In formula (4), L is the following formula (3):

The nitrogen atom containing cyclic compound represented by these is represented.

L ¹¹ , L ¹² , L ¹³ and L ¹⁴ represent a nitrogen atom-containing heterocyclyl group which may have a substituent. A ¹¹ , A ¹² , A ¹³ and A ¹⁴ represent a hydrocarbondiyl group which may have a substituent. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ represent a hydrocarbondiyl group which may have a substituent. Specific examples and preferred examples of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , L ¹¹ , L ¹² , L ¹³ and L ^14, and A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are included in the above device. This is the same as the description in Formula (3) regarding the metal complex.

  X represents a counter ion, and L ′ represents a bidentate or lower ligand other than the nitrogen atom-containing cyclic compound represented by the above formula (3). a is a number exceeding 0.5, and b and c are 0 or more. Specific examples and preferred examples of the counter ion (X) and the ligand (L ′) are the same as those in the formula (11) regarding the metal complex contained in the device.

  In the formula (4), a, b and c are determined by the number of coordination atoms of the ligand and the charging ratio at the time of synthesis. a is a number exceeding 0.5, preferably 0.5 <a <1.5, more preferably 0.7 <a <1.2, and even more preferably 0. .9 <a <1.1. b is a number of 0 or more, preferably a number satisfying 0 ≦ b ≦ 4, more preferably a number satisfying 0 ≦ b ≦ 3. c is a number of 0 or more, preferably a number satisfying 0 ≦ c ≦ 6, more preferably a number satisfying 0 ≦ c ≦ 3, and still more preferably a number satisfying 0 ≦ c ≦ 2. Particularly preferably 0.

Ａ¹¹、Ａ¹²、Ａ¹³及びＡ¹⁴は、置換基を有していてもよいヒドロカーボンジイル基を表す。Ａ¹¹、Ａ¹²、Ａ¹³及びＡ¹⁴はそれぞれ同一であっても異なっていてもよい。Ｒ²¹、Ｒ²²、Ｒ²³及びＲ²⁴は、水素原子又は置換基を有していてもよいヒドロカルビル基を表す。Ｒ²¹、Ｒ²²、Ｒ²³及びＲ²⁴はそれぞれ同一であっても異なっていてもよい。 The present invention provides a nitrogen atom-containing cyclic compound represented by the following formula (5).

A ¹¹ , A ¹² , A ¹³ and A ¹⁴ represent a hydrocarbondiyl group which may have a substituent. A ¹¹ , A ¹² , A ¹³ and A ¹⁴ may be the same or different. R ²¹ , R ²² , R ²³ and R ²⁴ represent a hydrogen atom or a hydrocarbyl group which may have a substituent. R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different.

Specific examples and preferred examples of A ¹¹ , A ¹² , A ¹³ , A ¹⁴ , R ²¹ , R ²² , R ^23, and R ²⁴ are the same as those described in Formula (5) regarding the metal complex included in the element. is there.

  Since the metal complex of the present invention is useful as a magnetic material, it is also useful as a biological probe and a contrast agent. The metal complex of the present invention is also useful as a material for additives, modifiers, catalysts and the like. Furthermore, the nitrogen atom-containing cyclic compound of the present invention is useful as a ligand for the metal complex.

  Hereinafter, the present invention will be described in detail with reference to examples.

  The UV-visible absorption spectrum was determined by measuring with an absorption spectrophotometer (Varian, Cary 5E). The emission spectrum was measured with a fluorescence spectrophotometer (trade name: FP-6500, manufactured by JASCO Corporation) with an excitation wavelength of 389 nm. The luminescence quantum yield was calculated in comparison with the luminescence quantum yield (55%) in the standard sample quinine sulfate 1N sulfuric acid aqueous solution. The excitation lifetime was determined as the excitation lifetime at the emission peak wavelength of the emission spectrum with a fluorescence spectrophotometer (manufactured by JOBINYVON-SPEX, trade name: Fluorolog-Tau3).

原料の２−（クロロメチル）−１−メチルベンズイミダゾールは、Ｉｎｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ ３２，２０５６−２０６７（１９９３）の記載に準じて合成した。すなわち、Ｎ−メチル−１，２−ジアミノベンゼンとクロロ酢酸を６Ｎ塩酸中にて８時間加熱還流し反応させ、アンモニア水にて中和することにより、２−（クロロメチル）−１−メチルベンズイミダゾールを得た。 <Example 1>
<Synthesis example of nitrogen atom-containing cyclic compound (A-13)>

The starting material, 2- (chloromethyl) -1-methylbenzimidazole, was synthesized according to the description of Inorganic Chemistry 32, 2056-2067 (1993). That is, N-methyl-1,2-diaminobenzene and chloroacetic acid were reacted by heating under reflux in 6N hydrochloric acid for 8 hours, and neutralized with aqueous ammonia to give 2- (chloromethyl) -1-methylbenzen. Imidazole was obtained.

  To a 50 mL Schlenk tube, 2- (chloromethyl) -1-methylbenzimidazole (500 mg, 2.77 mmol), 1,4,7,10-tetraazacyclododecane (114 mg, 0.660 mmol), anhydrous sodium carbonate ( 294 mg, 2.77 mmol) and N, N-dimethylformamide (DMF, 10 mL) were added, and the mixture was heated and stirred at 100 ° C. for 13 hours under an argon atmosphere. The solvent was distilled off under vacuum, and the residue was purified by alumina column chromatography to obtain a white solid nitrogen atom-containing cyclic compound (A-13) (213 mg, yield 47%).

¹ H NMR (300 MHz, CDCl ₃ / MeOD-d ₄ ): δ (ppm) = 7.66 (d, J = 6.9 Hz, 4H), 7.27 (m, 12H), 3.67 (s, 8H), 3.39 (s, 12H), 2.76 (s, 16H).

窒素原子含有環式化合物（Ａ−１３）（２０ｍｇ、０．０２９ｍｍｏｌ）のアセトニトリル懸濁溶液（４ｍＬ）に、セリウムトリフルオロメタンスルホネート（１５ｍｇ、０．０２６ｍｍｏｌ）のエタノール溶液（４ｍＬ）を加えて、室温で１．５時間撹拌し、均一透明溶液を得た。ここにゆっくりとジエチルエーテル（約６ｍＬ）を加えて放置したところ、固体が析出した。この固体を回収し、真空下にて乾燥させ、白色固体の金属錯体（Ｂ−１）を得た（２３ｍｇ、収率７０％）。 <Synthesis Example of Metal Complex (B-1)>

An ethanol solution (4 mL) of cerium trifluoromethanesulfonate (15 mg, 0.026 mmol) was added to an acetonitrile suspension solution (4 mL) of the nitrogen atom-containing cyclic compound (A-13) (20 mg, 0.029 mmol), and And stirred for 1.5 hours to obtain a homogeneous transparent solution. When diethyl ether (about 6 mL) was slowly added and allowed to stand, a solid precipitated. This solid was collected and dried under vacuum to obtain a white solid metal complex (B-1) (23 mg, 70% yield).

  Elemental analysis Found (%) C: 46.15, H: 4.71, N: 13.81, S: 6.89, Calcd for metal complex (B-1) (%) C: 46.32, H: 4.37, N: 14.00, S: 6.16

原料の窒素原子含有環式化合物（Ａ−９）は、Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ，Ｄａｌｔｏｎ Ｔｒａｎｓａｃｔｉｏｎｓ １７４３−１７４５（１９８６）の記載に準じて合成した。すなわち、１，４，７，１０−テトラアザシクロドデカンと２−（クロロメチル）ピリジン塩酸塩を、水酸化ナトリウム存在下、ジクロロメタン中にて室温下２４時間反応させ、窒素原子含有環式化合物（Ａ−９）（不純物としてＨＣｌを含む）を得た。 <Example 2>
<Synthesis Example of Metal Complex (B-2)>

The starting nitrogen atom-containing cyclic compound (A-9) was synthesized according to the description in Journal of the Chemical Society, Dalton Transactions 1743-1745 (1986). That is, 1,4,7,10-tetraazacyclododecane and 2- (chloromethyl) pyridine hydrochloride were reacted in dichloromethane in the presence of sodium hydroxide for 24 hours at room temperature, and a nitrogen atom-containing cyclic compound ( A-9) (containing HCl as an impurity) was obtained.

  Dehydrated methanol (25 mL) was added to a nitrogen atom-containing cyclic compound (A-9) (500 mg, 0.932 mmol or less) and cerium trifluoromethanesulfonate (547 mg, 0.932 mmol), and the mixture was heated to reflux for 5 hours. When the reaction solution was slowly heated and concentrated at room temperature, colorless crystals were precipitated. The crystals were collected and dried under vacuum to obtain a metal complex (B-2) (335 mg, yield 34%).

  Elemental analysis Found (%) C: 39.26, H: 3.94, N: 10.71, S: 7.00, Cl: 3.04, Calcd for metal complex (B-2) (%) C: 39.51, H: 3.86, N: 10.64, S: 7.08, Cl: 2.35

  The metal complex (B-2) emitted yellowish green light in a solid powder state and a solution state (acetonitrile) by ultraviolet excitation (365 nm).

  The emission spectrum in acetonitrile had a peak at 475 nm, the emission quantum yield was 12%, and the excitation lifetime was 26.3 ns.

<Example of production of electroluminescent element>
A glass substrate on which an ITO film is formed with a thickness of 150 nm by a sputtering method is mixed with poly (2-hydroxyethyl methacrylate) (weight average molecular weight Mw 20000 or less) and 50% by weight of a metal complex (B-2). A film was formed by a coating method. The thickness was 120 nm. The formed film was dried at 60 ° C. for 20 minutes, and then lithium fluoride was deposited at about 0.5 nm and aluminum was further deposited at about 80 nm to form a cathode to produce an electroluminescent device. When voltage was applied to the resulting device, yellow-green light emission was observed.

  As a heteroatom, a cerium complex of a cyclic compound containing only an oxygen atom in the skeleton exhibits an emission peak at around 376 nm by ultraviolet light excitation, and an emission peak at around 382 nm by an electroluminescent element using the cerium complex (Solid-State Electronics. 51, 894-899 (2007)). That is, a cerium complex of a cyclic compound containing only oxygen atoms in the skeleton exhibits light emission in the ultraviolet region. In contrast, the electroluminescent device of the present invention containing a metal complex containing cerium and the nitrogen atom-containing cyclic compound has a light emission peak located in the visible light region as shown in the above examples, and visible light. Shows sufficient light emission in the region.

Claims (7)

An electroluminescent device comprising a metal complex of cerium and a nitrogen atom-containing cyclic compound represented by the following formula ( 2 ).

(Wherein, A ² and A ^3, .A ² and A ³ good .A ² also each be the same or different representing a good hydro carbon diyl group which may have a substituent, respectively If a same there are several good .A ³ be different also, good .Z ² be a plurality of a ³ are optionally substituted by one or more identical, -O -, - S-, or -NR ¹ - If .Z ² there are a plurality representing a good .m be different even plurality of Z ² are the same represents an integer of 2 to 6, p represents an integer of 0 or more, m + p is R is an integer of 3 or more, R ¹⁰ represents a hydrocarbondiyl group which may have a substituent, R ¹⁰ may be the same or different, and L ¹⁰ is represented by the following formula (6): ) .L ¹⁰ represents a group selected from groups represented by - (10) also have each be the same or different It has.)

(In formula (6), R ³ represents a hydrogen atom or a hydrocarbyl group which may have a substituent, R ⁴ represents a substituent, and e is an integer of 0 to 2. R ³ When the nitrogen atom to which R ⁴ is bonded and the carbon atom to which R ⁴ is bonded are adjacent to each other, R ³ and R ⁴ may be bonded to form a ring, and e is 2, and two R ^{When 4} is bonded to adjacent carbon atoms, two R ⁴ may be bonded to form a ring, and when e is 2, two R ⁴ may be the same May be different.)

(In Formula (7), R ⁵ represents a substituent, and f is an integer of 0 to 3. f is an integer of 2 or more, and a plurality of R ⁵ are bonded to adjacent carbon atoms. A plurality of R ⁵ may be bonded to form a ring, and when f is an integer of 2 or more, the plurality of R ⁵ may be the same or different.

(In the formula (8), X ¹ represents an oxygen atom, a sulfur atom, or -NR ⁶ - and is, R ⁶ represents a hydrocarbyl group which may have a hydrogen atom or a substituent, R ⁷ is Represents a substituent, and g is an integer of 0 to 2. When the nitrogen atom to which R ⁶ is bonded and the carbon atom to which R ⁷ is bonded are adjacent to each other, R ⁶ and R ⁷ are bonded to each other. an optionally form a ring .g 2, when two R ⁷ are respectively bonded to adjacent carbon atoms together, the two R ⁷ may form a ring. When g is 2, two R ^{7 s} may be the same or different.)

(In Formula (9), R ⁸ represents a substituent, and h is an integer of 0 to 3. h is an integer of 2 or more, and a plurality of R ⁸ are bonded to adjacent carbon atoms. A plurality of R ⁸ may be bonded to form a ring, and when h is an integer of 2 or more, the plurality of R ⁸ may be the same or different.

(In Formula (10), R ⁹ represents a substituent, and i is an integer of 0 to 4. i is an integer of 2 or more, and a plurality of R ⁹ are bonded to adjacent carbon atoms. A plurality of R ⁹ may combine to form a ring.) The electroluminescent element according to claim 1 , wherein in the formula (2), m + p is an integer of 3 to 6. In the above formula (2), electroluminescent device according to claim 1 or 2 p is 0. Nitrogen-containing cyclic compound represented by the following formula (3), electroluminescent device according to any one of claims 1 to 3.

(In the formula, L ¹¹ , L ¹² , L ¹³ and L ¹⁴ represent groups selected from the groups represented by the formulas (6) to (10). L ¹¹ , L ¹² , L ¹³ and L ¹⁴ represent A ¹¹ , A ¹² , A ¹³ and A ¹⁴ each represent a hydrocarbondiyl group which may have a substituent, A ¹¹ , A ¹² , A ¹³ and A ¹⁴ may be the same or different, and R ¹¹ , R ¹² , R ^13, and R ¹⁴ each represents an optionally substituted hydrocarbondiyl group, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be the same or different. The electroluminescent element according to claim 4 , wherein the metal complex is a metal complex represented by the following composition formula (11).

(In the formula, L represents a nitrogen atom-containing cyclic compound represented by the following formula (3). When there are a plurality of L, the plurality of L may be the same or different. X is a counter ion. If .X representing the there are a plurality, respectively, which may be be different also. a same plurality of X 'is a positive number, b' is a number of 0 or more.)

(In the formula, L ¹¹ , L ¹² , L ¹³ and L ¹⁴ represent groups selected from the groups represented by the formulas (6) to (10). L ¹¹ , L ¹² , L ¹³ and L ¹⁴ represent A ¹¹ , A ¹² , A ¹³ and A ¹⁴ each represent a hydrocarbondiyl group which may have a substituent, A ¹¹ , A ¹² , A ¹³ and A ¹⁴ may be the same or different, and R ¹¹ , R ¹² , R ^13, and R ¹⁴ each represents an optionally substituted hydrocarbondiyl group, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be the same or different. A metal complex represented by the following composition formula (4).

(In the formula, L represents a nitrogen atom-containing cyclic compound represented by the following formula (3). When there are a plurality of L, the plurality of L may be the same or different. X is a counter ion. If .X representing the there are a plurality, the plurality of X but it may also be optionally substituted by one or more identical respectively .a is a number greater than 0.5, b is a number of 0 or more.)

^{(Wherein, L 11, L 12, L} 13 and L ^{14 are, .L 11, L 12, L} 13 and L ¹⁴ represents a group selected from groups represented by the following formula (6) to (10) A ¹¹ , A ¹² , A ¹³ and A ¹⁴ each represent a hydrocarbondiyl group which may have a substituent, A ¹¹ , A ¹² , A ¹³ and A ¹⁴ may be the same or different, and R ¹¹ , R ¹² , R ^13, and R ¹⁴ each represents an optionally substituted hydrocarbondiyl group, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be the same or different.

(In formula (6), R ³ represents a hydrogen atom or a hydrocarbyl group which may have a substituent, R ⁴ represents a substituent, and e is an integer of 0 to 2. R ³ When the nitrogen atom to which R ⁴ is bonded and the carbon atom to which R ⁴ is bonded are adjacent to each other, R ³ and R ⁴ may be bonded to form a ring, and e is 2, and two R ^{When 4} is bonded to adjacent carbon atoms, two R ⁴ may be bonded to form a ring, and when e is 2, two R ⁴ may be the same May be different.)

(In Formula (7), R ⁵ represents a substituent, and f is an integer of 0 to 3. f is an integer of 2 or more, and a plurality of R ⁵ are bonded to adjacent carbon atoms. A plurality of R ⁵ may be bonded to form a ring, and when f is an integer of 2 or more, the plurality of R ⁵ may be the same or different.

(In the formula (8), X ¹ represents an oxygen atom, a sulfur atom, or -NR ⁶ - and is, R ⁶ represents a hydrocarbyl group which may have a hydrogen atom or a substituent, R ⁷ is Represents a substituent, and g is an integer of 0 to 2. When the nitrogen atom to which R ⁶ is bonded and the carbon atom to which R ⁷ is bonded are adjacent to each other, R ⁶ and R ⁷ are bonded to each other. an optionally form a ring .g 2, when two R ⁷ are respectively bonded to adjacent carbon atoms together, the two R ⁷ may form a ring. When g is 2, two R ^{7 s} may be the same or different.)

(In Formula (9), R ⁸ represents a substituent, and h is an integer of 0 to 3. h is an integer of 2 or more, and a plurality of R ⁸ are bonded to adjacent carbon atoms. A plurality of R ⁸ may be bonded to form a ring, and when h is an integer of 2 or more, the plurality of R ⁸ may be the same or different.

(In Formula (10), R ⁹ represents a substituent, and i is an integer of 0 to 4. i is an integer of 2 or more, and a plurality of R ⁹ are bonded to adjacent carbon atoms. A plurality of R ⁹ may combine to form a ring.) A nitrogen atom-containing cyclic compound represented by the following formula (5).

(In the formula, A ¹¹ , A ¹² , A ¹³ and A ¹⁴ represent a hydrocarbondiyl group which may have a substituent. A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are the same, respectively. R ²¹ , R ²² , R ²³ and R ^{24 each} represents a hydrogen atom or a hydrocarbyl group which may have a substituent, wherein R ²¹ , R ²² , R ²³ and R ²⁴ are each They may be the same or different.)