JP7100312B2 - New cerium complex and luminescent material - Google Patents

Description

The present invention relates to a novel cerium carbene complex, a method for producing the same, a cerium carbene complex composition containing the same, a light emitting material, and its use.

Currently, as a fluorescent material for LED lighting and an organic EL light emitting layer material, an inorganic fluorescent material such as YAG and a phosphorescent material such as an Ir complex are used.
In LED lighting, high-output LED elements such as purple and ultraviolet light source LED elements, and high-brightness and high-color-playing LED lighting using blue, green, and red (RGB) phosphors are required.
On the other hand, in organic EL displays and lighting, expensive metals such as Ir are used as phosphorescent dopants for RGB light emitting layers, which are highly durable and do not undergo quenching due to damage to the light emitting layer of oxygen and water vapor invading from high current environments and gas barrier layers. It is hoped that it will be realized without.

Further, since high-power LED elements such as ultraviolet LEDs generate significant heat generation, there is a demand for highly heat-resistant light-emitting materials that can withstand thermal deterioration, and also for organic EL elements that can withstand high-temperature processes such as electrode formation.
In order to improve the efficiency of solar cells and the productivity of agricultural facilities, a wavelength conversion film made by adding a light emitting material such as a phosphor to EVA, LDPE, and LLDPE has been proposed. There are many problems in terms of UV resistance, oxidation resistance, moisture resistance, and manufacturing cost, and it has not been put into practical use.

The cerium complex can emit blue, green, and red RGB by controlling the 4f-5d transition with a ligand. In Non-Patent Document 1, a Ce complex having a cyclopentadienyl ligand or a pentamethylcyclopentadienyl ligand emits light in purple (408 nm), blue (458 nm), green (544 nm), and red (628 nm). I am reporting that. Further, Non-Patent Document 2 and Non-Patent Document 3 report that a Ce complex having a tris (benzimidazol-2-ylmethyl) amine ligand emits light in blue (about 450 nm) by ultraviolet excitation. Further, Patent Document 1 reports that a Ce complex having a trispyridylpyrazole volate ligand emits green light (529 nm) by ultraviolet excitation. However, there has been no proposal that these Ce complexes are unstable in the atmosphere and have practical performance, durability, life, and manufacturing cost.

Further, in order to improve the quantum yield, turnover and durability of the photocatalyst for redox reaction, which is being researched for the purpose of artificial photosynthesis, it is desired to improve the performance and durability of the photosensitizer. ..
That is, in the Ce complex proposed so far, light resistance (UV resistance) is used for LEDs, organic EL, films for solar cells, films for agricultural facilities, and photosensitizers for photocatalysts for redox reactions. The performance is insufficient in terms of weather resistance, heat resistance, and durability, and improvement is desired.

Japanese Unexamined Patent Publication No. 2012-246230

Organometallics 6,913 (1987) Angew. Chem. Int. Ed. 46,7399 (2007) Chem. Let. 43,1496 (2014)

The present invention has been made in view of the above problems, and an object thereof is a phosphor for LED, an organic EL light emitting layer material, a wavelength conversion film for solar cells, a wavelength conversion film for agricultural facilities, and a photocatalyst for redox reaction. To provide a cerium complex suitable for use as a sensitizer, a composition containing the same, and to provide an LED device, an organic EL device, a solar cell device, a film for an agricultural facility, and a photocatalyst for a redox reaction using the cerium complex. It is in.

The present inventors have a cerium complex having a specific structure and a composition containing the same having high light resistance (UV resistance), weather resistance, heat resistance, and durability, and LED devices such as phosphors for LEDs and organic materials. Suitable as a photosensitizer for organic EL devices such as EL light emitting layer materials, solar cell devices such as wavelength conversion materials for solar cells, films for agricultural facilities such as wavelength conversion materials for agricultural facilities, and photocatalysts for redox reactions. The present invention was completed.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０は、水素原子、ヒドロキシ基、カルボキシル基、ホスホン酸基、炭素数１～２０の炭化水素基、又は、酸素原子若しくはリン原子を含有する炭化水素基を表し、それらは互いに結合して環を形成していてもよい。Ｒ^１１，Ｒ^１２は、水素原子、又は炭素数１～２０の炭化水素基を表し、それらは互いに結合して環を形成していてもよい。ｘは０～１０の整数を表す。） That is, the gist of the present invention is as follows.
(1) A cerium complex containing a trivalent cerium and a carbene compound.
(2) The cerium complex according to (1) above, wherein the carbene compound is represented by the following formula (1).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are hydrogen atoms, hydroxy groups, carboxyl groups, phosphonic acid groups, and carbon atoms. It represents 1 to 20 hydrogen groups or a hydrocarbon group containing an oxygen atom or a phosphorus atom, and they may be bonded to each other to form a ring. R ¹¹ and R ¹² are hydrogen atoms or hydrogen atoms or It represents a hydrocarbon group having 1 to 20 carbon atoms, and they may be bonded to each other to form a ring. X represents an integer of 0 to 10).

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、ｘは、式（１）における定義と同じである。ｎは、１以上の整数を表す。Ｌは、ハロゲン、シラザン、スルホン酸、又はβ－ジケトンのアニオンを表す。）
（４）Ｒ^１，Ｒ^２，Ｒ^３，Ｒ^４，Ｒ^５，Ｒ^６，Ｒ^７，Ｒ^８，Ｒ^９，Ｒ^１０が水素原子、アルキル基、ヒドロキシ基又はホスフィンオキシド基である、上記（２）又は（３）に記載のセリウム錯体。
（５）カルベン化合物が、ホスフィニル基を有するイミダゾリリデンカルベン化合物である、上記（１）～（４）のいずれかに記載のセリウム錯体。 (3) The cerium complex according to (1) or (2) above, which is represented by the following formula (2).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and x are the definitions in formula (1). The same. N represents an integer of 1 or more. L represents an anion of halogen, silazane, sulfonic acid, or β-diketone.)
(4) R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are hydrogen atoms, alkyl groups, hydroxy groups, or phosphine oxide groups. 2) or the cerium complex according to (3).
(5) The cerium complex according to any one of (1) to (4) above, wherein the carbene compound is an imidazolidene carbene compound having a phosphinyl group.

(6) The cerium complex according to (5) above, wherein the imidazolidene carbene compound having a phosphinyl group is a compound represented by the following formula (5).

（８）上記（１）～（７）のいずれかに記載のセリウム錯体の製造方法であり、三価のセリウム塩、その無水物、又は水和物と、カルベン化合物とを、不活性溶媒中で反応させるセリウム錯体の製造方法。 (7) The cerium complex according to any one of (1) to (4) above, wherein the carbene compound is a compound represented by the following formula (3) or the following formula (4).

(8) The method for producing a cerium complex according to any one of (1) to (7) above, wherein a trivalent cerium salt, an anhydrate or a hydrate thereof, and a carben compound are mixed in an inert solvent. A method for producing a cerium complex to be reacted with.

（式中、Ｒ^１７は、炭素数１～２０の炭化水素基を表し、２つ以上のＲ^１７は互いに結合しても良い。） (9) The trivalent cerium salt is 2,4-pentandionatocerium (III), trifluoroacetylacetonatocerium (III), 6,6,7,7,8,8,8-heptafluoro-2. , 2-dimethyl-3,5-octanedionatocerium (III), cerium trifluoromethanesulfonate (III), 1,2,3,4-tetramethyl-2,4-cyclopentadienylcerium (III), Alternatively, the method for producing a cerium complex according to (8) above, which is a cerium anion-coordinating cerium compound represented by the following formula (8).

(In the formula, R ¹⁷ represents a hydrocarbon group having 1 to 20 carbon atoms, and two or more R ¹⁷ may be bonded to each other.)

(10) A cerium complex composition containing the cerium complex according to any one of (1) to (7) above.
(11) A light emitting material made of the cerium complex according to any one of (1) to (7) above.
(12) A luminescent material comprising the cerium complex composition according to (10) above.
(13) The light emitting material according to (11) or (12) above, which is excited by ultraviolet light or visible light and emits blue light.
(14) A photosensitizer for an LED device, an organic EL device, a solar cell device, a film for an agricultural facility, or a photocatalyst for a redox reaction, which comprises the light emitting material according to the above (11) or (12).
(15) An imidazolium halide compound having a phosphinyl group.
(16) The imidazolium halide compound having a phosphinyl group according to (15) above, wherein the imidazolium halide compound having a phosphinyl group is 1,3-bis (2- (diphenylphosphinyl) benzyl) imidazolium bromide.
(17) An imidazolidene carbene compound having a phosphinyl group.

（１９）上記（１５）又は（１６）に記載のホスフィニル基を有するイミダゾリウムハライド化合物の製造方法であり、ホスフィニル基を有する芳香族ハライド化合物とイミダゾール化合物を反応させることを特徴とする製造方法。
（２０）上記（１７）又は（１８）に記載のホスフィニル基を有するイミダゾリリデンカルベン化合物の製造方法であり、ホスフィニル基を有するイミダゾリウムハライド化合物からハロゲン化水素を脱離反応させることを特徴とする製造方法。 (18) The phosphinyl group according to (17) above, wherein the imidazolidene carbene compound having a phosphinyl group is 1,3-bis (2- (diphenylphosphinyl) benzyl) imidazolidene of the following formula (5). Imidazole lidene carbene compound having.

(19) The method for producing an imidazolium halide compound having a phosphinyl group according to (15) or (16) above, which comprises reacting an aromatic halide compound having a phosphinyl group with an imidazole compound.
(20) The method for producing an imidazolidene carbene compound having a phosphinyl group according to (17) or (18) above, characterized in that hydrogen halide is desorbed from the imidazolium halide compound having a phosphinyl group. Manufacturing method.

The cerium complex containing the trivalent cerium and the carben compound of the present invention and the cerium complex composition containing the cerium complex can be used as a light emitting material such as a light emitting material and a wavelength conversion material, and have light resistance (UV resistance) and weather resistance. It is possible to provide an LED device, an organic EL device, a solar cell device, a film for an agricultural facility, a photosensitizer for a photocatalyst for a redox reaction, and the like, which have good properties, heat resistance, durability, and the like.

The present invention is a cerium complex containing trivalent cerium and a carbene compound, and a preferable cerium complex of the present invention includes trivalent cerium and a carbene compound represented by the following formula (1).

In the above formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ (sometimes referred to as R ¹ to R ¹⁰ ), hydrogen. Represents an atom, a hydroxy group, a carboxyl group, a phosphonic acid group, or a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group containing an oxygen atom or a phosphorus atom, which are bonded to each other to form a ring. May be. R ¹¹ and R ¹² represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be bonded to each other to form a ring. x represents an integer from 0 to 10.

上記式（２）中、Ｒ^１～Ｒ^１０、ｘは、上記式（１）における定義と同じである。ｎは、１以上の整数を表す。Ｌは、ハロゲン、シラザン、スルホン酸又はβ－ジケトンのアニオンを表す。 The preferred cerium complex of the present invention is represented by the following formula (2).

In the above formula (2), R ¹ to R ¹⁰ , x are the same as the definitions in the above formula (1). n represents an integer of 1 or more. L represents an anion of halogen, silazane, sulfonic acid or β-diketone.

In the above formulas (1) and (2), R ¹ to R ¹⁰ are preferably alkyl groups, aryl groups, arylalkyl groups, alkylaryl groups, alkenyl groups or alkynyl groups having 1 to 10 carbon atoms. be.
Examples of R ¹ to R ¹⁰ include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, and tert. -Butyl, cyclobutyl, n-pentyl, tert. -Amil, cyclopentyl, n-hexyl, cyclohexyl, methylcyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, Alkyl groups such as n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 1-adamantyl; aryl groups such as phenyl, naphthyl and anthracenyl; arylalkyls such as benzyl and phenylethyl Group; Alkyl aryl group such as toluyl, xylenyl, ethylphenyl, isopropylphenyl, butylphenyl; Alkyl group such as vinyl, propenyl, cyclobutenyl, cyclopentadienyl, cyclohexenyl, cyclooctenyl, cyclooctadienyl; acetylynyl group, propynyl, etc. The alkynyl group of the above can be mentioned.

R ¹ to R ¹⁰ are linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and n-heptyl having 7 or less carbon atoms; isopropyl, i. -Butyl, sec-Butyl, tert. -Butyl, tert. -A branched chain alkyl group such as amyl; a cyclic alkyl group such as cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl; a cyclic alkenyl group such as cyclobutenyl, cyclopentadienyl, cyclohexenyl; or a cyclic aryl group such as phenyl, toluyl preferable. Particularly preferred are linear alkyl groups having 4 or less carbon atoms such as methyl, ethyl, n-propyl, n-butyl; or isopropyl, i-butyl, sec-butyl, tert. -A branched chain alkyl group having 4 or less carbon atoms such as butyl.

When R ¹ to R ¹⁰ are hydrocarbon groups containing an oxygen atom, R ¹ to R ¹⁰ are preferably an alkoxy group, an aryloxy group, an arylacoxy group, or an alkyl having 1 to 20 carbon atoms. It is an aryloxy group, an alkenyloxy group, an alkynyloxy group, or the like. Specifically, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, i-butoxy, sec-butoxy, tert. -Butoxy, cyclobutoxy, n-pentoxy, tert. -Amyroxy, cyclopentoxy, n-hexyloxy, cyclohexyloxy, methylcyclohexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n- Dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadesyloxy, n-eicosyloxy, 1- Alkoxy groups such as adamantyloxy; aryloxy groups such as phenyloxy, naphthyloxy and anthracenyloxy; arylacoxy groups such as benzyloxy and phenylethoxy; toluyloxy, xylenyloxy, ethylphenyloxy, isopropylphenyloxy and butylphenyl Alkylaryloxy groups such as oxy; alkenyloxy groups such as propenyloxy, cyclobutenyloxy, cyclopentadienyloxy, cyclohexenyloxy, cyclooctenyloxy, cyclooctadienyloxy; alkynyloxy groups such as propynyloxy, etc. Can be raised.

Among the above, linear alkoxy groups having 7 or less carbon atoms such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, n-heptyloxy; isopropoxy, i- Butoxy, sec-butoxy, tert. -Butoxy, tert. -Branched chain alkoxy group such as amyroxy; cyclic alkoxy group such as cyclobutoxy, cyclopentoxy, cyclohexyloxy, methylcyclohexyloxy; cyclic alkenyloxy group such as cyclobutenyloxy, cyclopentadienyloxy, cyclohexenyloxy; Cyclic aryloxy groups such as phenyloxy and toluyloxy are preferred. Particularly preferably, linear alkoxy groups such as methoxy, ethoxy, n-propoxy, n-butoxy having 4 or less carbon atoms; isopropoxy, i-butoxy, sec-butoxy, tert. -A branched chain alkoxy group such as butoxy.

R ¹ to R ¹⁰ may be bonded to each other to form a cyclic group such as phenylene, naphthylene, or cyclohexylene. As the cyclic group, phenylene, cyclohexylene and the like are preferable, and phenylene and the like are particularly preferable.

When R ¹ to R ¹⁰ are hydrocarbon groups having a phosphorus atom, R ¹ to R ¹⁰ are preferably a phosphino group represented by the following formula (6) or a phosphinyl group represented by the following formula (7). Can be mentioned.

上記式（６）、式（７）において、Ｒ^１３，Ｒ^１４、Ｒ^１５，Ｒ^１６は、炭素数１～２０の炭化水素基、又は酸素原子、窒素原子若しくはハロゲン原子を有する炭化水素基を表す。Ｒ^１３，Ｒ^１４は、同一であっても、異なってもよい。

In the above formulas (6) and (7), R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ have a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having an oxygen atom, a nitrogen atom or a halogen atom. show. R ¹³ and R ¹⁴ may be the same or different.

Specific examples of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert. -Amil, cyclopentyl, n-hexyl, cyclohexyl, methylcyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, adamantyl, n-undecyl, n-dodecyl, n-tridecyl, n- Hydrocarbon groups such as tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecil, n-eicosyl; cyclobutenyl, cyclopentadienyl, cyclohexenyl, cyclooctenyl, cyclooctadienyl, 1- Hydrocarbon groups such as adamantyl, phenyl, trill, xylyl, ethylphenyl, isopropylphenyl, butylphenyl, naphthyl, anthracenyl, benzyl, phenylethyl; methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, phenoxy, phenyldioxy, o. -Oxygen atom-containing hydrocarbon groups such as methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, 2,6-dimethoxyphenyl, 2-furyl; o-fluorophenyl, m-fluorophenyl, p-fluorophenyl, pentafluoro Phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-bromophenyl, m-bromophenyl, p-bromophenyl, o-iodophenyl, m-iodophenyl, p-iodophenyl, 3,5-bis ( Halogen atom-containing hydrocarbon group such as trifluoromethyl) phenyl; nitrogen atom such as o-dimethylaminophenyl, m-dimethylaminophenyl, p-dimethylaminophenyl, o-diethylaminophenyl, m-diethylaminophenyl, p-diethylaminophenyl Examples include the contained hydrocarbon group.

Among these, R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are hydrocarbon groups such as phenyl, trill, xylyl, ethylphenyl, isopropylphenyl, butylphenyl, naphthyl, anthracenyl, benzyl, and phenylethyl, o-fluorophenyl, and so on. m-fluorophenyl, p-fluorophenyl, pentafluorophenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-bromophenyl, m-bromophenyl, p-bromophenyl, o-iodophenyl, m-iodophenyl , P-Iodophenyl, 3,5-bis (trifluoromethyl) phenyl and other halogen atom-containing hydrocarbon groups are preferred. Particularly preferred are phenyl, trill, o-fluorophenyl, m-fluorophenyl, p-fluorophenyl, pentafluorophenyl and the like.

Specific examples of the phosphino group represented by the above formula (6) include dimethylphosphino, diethylphosphino, din-propylphosphino, diisopropylphosphino, din-butylphosphino, diisobutylphosphino, and disec-. Butylphosphino, tert. -Butyl phosphino, dicyclobutyl phosphino, di-n-pentyl phosphino, ditert. -Amilphosphino, dicyclopentylphosphino, din-hexylphosphino, din-octylphosphino, dicyclohexylphosphino, di (methylcyclohexyl) phosphino, din-heptylphosphino, dicyclobutenylphosphino, dicyclopenta Dienylphosphino, dicyclohexenylphosphino, diphenylphosphino, ditoluylphosphino, tri-o-tolylphosphino, tri-m-tolylphosphino, tri-p-tolylphosphino, trichenylphosphino, tris (2-methoxyphenyl) ) Phosphino, Tris (4-methoxyphenyl) phosphino, Tris (2,6-dimethoxyphenyl) phosphino, Tris (2-furyl) phosphino, Tris (4-dimethylaminophenyl) phosphino, dixylenylphosphino, diethylphenylphos Fino, Diisopropylphenylphosphino, Dibutylphenylphosphino, Dinaphthylphosphino, Dianthrasenylphosphino, Dibenzylphosphino, Di (phenylethyl) phosphino, Ethylphenylphosphino, tert. -Butylphenylphosphino, cyclohexylphenylphosphino, cyclohexylphenylphosphino, phenylmethylphosphino, phenylethylphosphino, phenylisopropylphosphino, phenylcyclohexylphosphino, phenyl-2-pyridylphosphino, diphenyl-1-pyrenyl Phenyl, tert. -Butyl (dimethylaminophenyl) phosphino, tert. -Butyl (3-methyl-2-butenyl) phosphino, (4-fluorophenyl) phenylphosphino, di (4-fluorophenyl) phosphino, (2-bromophenyl) phenylphosphino, (pentafluorophenyl) phenylphosphino , (Pentafluorophenyl) phenylphosphino, bis (pentafluorophenyl) phosphino, bis [(3,5-bis (trifluoromethyl) phenyl] phosphino and the like.

Specific examples of the phosphinyl group represented by the above formula (7) include dimethylphosphinyl, diethylphosphinyl, din-propylphosphinyl, diisopropylphosphinyl, din-butylphosphinyl, and diisobutylphos. Finyl, disec-butylphosphinyl, ditert. -Butylphosphinyl, dicyclobutylphosphinyl, din-pentylphosphinyl, ditert. -Amilphosphinyl, dicyclopentylphosphinyl, din-hexylphosphinyl, din-octylphosphinyl, dicyclohexylphosphinyl, di (methylcyclohexyl) phosphinyl, din-heptylphosphinyl, dicyclo Butenylphosphinyl, dicyclopentadienylphosphinyl, dicyclohexenylphosphinyl, diphenylphosphinyl, ditoluylphosphinyl, tri-o-tolylphosphinyl, tri-m-tolylphosphinyl, tri- p-tolylphosphinyl, trichenylphosphinyl, tris (2-methoxyphenyl) phosphinyl, tris (4-methoxyphenyl) phosphinyl, tris (2,6-dimethoxyphenyl) phosphinyl, tris (2-furyl) phosphinyl , Tris (4-dimethylaminophenyl) phosphinyl, dixylenyl phosphinyl, diethylphenylphosphinyl, diisopropylphenylphosphinyl, dibutylphenylphosphinyl, dinaphthylphosphinyl, dianthrasenylphosphinyl, di Benzylphosphinyl, di (phenylethyl) phosphino, ethylphenylphosphinyl, tert. -Butylphenylphosphinyl, cyclohexylphenylphosphinyl, cyclohexylphenylphosphinyl, phenylmethylphosphinyl, phenylethylphosphinyl, phenylisopropylphosphinyl, phenylcyclohexylphosphinyl, phenyl-2-pyridylphosphini Le, diphenyl-1-pyrenylphosphinyl, tert. -Butyl (dimethylaminophenyl) phosphinyl, tert. -Butyl (3-methyl-2-butenyl) phosphinyl, (4-fluorophenyl) phenylphosphinyl, di (4-fluorophenyl) phosphinyl, (2-bromophenyl) phenylphosphinyl, (pentafluorophenyl) phenyl Phsphinyl, (pentafluorophenyl) phenylphosphinyl, bis (pentafluorophenyl) phosphinyl, bis [(3,5-bis (trifluoromethyl) phenyl] phosphinyl and the like can be mentioned.

Among them, a phosphinyl group is preferable, and disec-butylphosphinyl, ditert. -Butylphosphinyl, dicyclobutylphosphinyl, din-pentylphosphinyl, ditert. -Amilphosphinyl, dicyclopentylphosphinyl, din-hexylphosphinyl, din-octylphosphinyl, dicyclohexylphosphinyl, di (methylcyclohexyl) phosphinyl, din-heptylphosphinyl, dicyclo Butenylphosphinyl, dicyclopentadienylphosphinyl, dicyclohexenylphosphinyl, diphenylphosphinyl, ditoluylphosphinyl, tri-o-tolylphosphinyl, tri-m-tolylphosphinyl, tri- p-tolylphosphinyl, trichenylphosphinyl, tris (2-methoxyphenyl) phosphinyl, tris (4-methoxyphenyl) phosphinyl, tris (2,6-dimethoxyphenyl) phosphinyl, tris (2-furyl) phosphinyl , Tris (4-dimethylaminophenyl) phosphinyl, dixylenyl phosphinyl, diethylphenylphosphinyl, diisopropylphenylphosphinyl, dibutylphenylphosphinyl, dinaphthylphosphinyl, dianthrasenylphosphinyl, di Benzylphosphinyl, di (phenylethyl) phosphino, ethylphenylphosphinyl, tert. -Butylphenylphosphinyl, cyclohexylphenylphosphinyl, cyclohexylphenylphosphinyl, phenylmethylphosphinyl, phenylethylphosphinyl, phenylisopropylphosphinyl, phenylcyclohexylphosphinyl, phenyl-2-pyridylphosphini Le, diphenyl-1-pyrenylphosphinyl, tert. -Butyl (dimethylaminophenyl) phosphinyl, tert. -Butyl (3-methyl-2-butenyl) phosphinyl, (4-fluorophenyl) phenylphosphinyl, di (4-fluorophenyl) phosphinyl, (2-bromophenyl) phenylphosphinyl, (pentafluorophenyl) phenyl Phenyl, (pentafluorophenyl) phenylphosphinyl, bis (pentafluorophenyl) phosphinyl, bis [(3,5-bis (trifluoromethyl) phenyl] phosphinyl.

As R ¹ to R ¹⁰ , a hydrogen atom, an alkyl group, a hydroxy group, or a phosphine oxide group is preferable, and a phosphine oxide group is particularly preferable.
In the above equations (1) and (2), x preferably represents an integer of 0 to 5, more preferably an integer of 0 to 3, and more preferably an integer of 0 or 1.

Specific examples of the carbene compound represented by the above formula (1) include imidazolilidene carbene compounds of the following formulas 1-1 to 1-23.

Among the above formulas 1-1 to 1-23, the 1,3-dimesitylimidazolidelencarbene compound represented by the following formula (3), which is represented by the formula 1-10, is preferable.

In addition, examples of the carbene compound represented by the formula (1) include imidazolilidene carbene compounds of the following formulas 1-24 to 1-27.

Among the above formulas 1-24 to 1-27, the 1,3-bis (3,5-di-tert.-butyl-2-hydroxy) represented by the following formula (4), which is represented by the above formula 1-26. Benzyl) Imidazole lidene carbene compounds are preferred.

Further, examples of the carbene compound represented by the formula (1) include an imidazolidene carbene compound having a phosphinyl group. Specific examples thereof include imidazolidene carbenes having a phosphinyl group of the following formulas 1-28 to 1-34.

In the above formulas 1-28 to 1-34, the 1,3-bis (2- (diphenylphosphinyl) benzyl) imidazolidene represented by the following formula (5) represented by the formula 1-28. 1,3-bis (3- (diphenylphosphinyl) benzyl) imidazolidene represented by formula 1-33, or 1,3-bis (4- (diphenylphosphinyl) benzyl) represented by formula 1-34. ) Imidazolidene is preferred.

Among the formulas 1-1 to 1-34 of the specific examples of the above formula (1), formulas 1-10 to 1-32 are preferable, and formulas 1-24 to 1-32 are particularly preferable. In particular, formulas 1-28 to 1-34, which are imidazolidene carbene compounds having a phosphinyl group, are preferable.

The cerium complex of the present invention contains trivalent cerium and a carbene compound, and the trivalent cerium and the carbene compound, which are the respective constituents, may be used alone or in combination of two or more.
The content of the trivalent cerium and the carbene compound in the cerium complex of the present invention is preferably 0.0001 to 1,000,000 mol, and particularly preferably 0.001 to 100,000 mol of the carbene compound with respect to 1 mol of the trivalent cerium. It is 000 mol.

The method for producing the cerium complex of the present invention will be described.
The cerium complex of the present invention is produced by reacting trivalent cerium with a carbene compound, but the specific means thereof is not particularly limited. For example, synthesizing a cerium complex containing trivalent cerium and a carbene compound by adding, mixing, and reacting a carbene compound with a solution in which a trivalent cerium salt is dissolved or dispersed in an inert solvent. Can be done.

Examples of the trivalent cerium salt include cerium fluoride (III), cerium chloride (III), cerium bromide (III), cerium iodide (III), cerium sulfate (III), and cerium nitrate (III). Cerium phosphate (III), cerium carbonate (III), cerium perchlorate (III), cerium acetate (III), cerium 2-ethylhexanate (III), cerium stearate (III), cerium oxalate (III) , 2,4-Pentandionatocerium (III), Trifluoroacetylacetonatocerium (III), 6,6,7,7,8,8,8-Heptafluoro-2,2-dimethyl-3,5- Uses anhydrides and hydrates such as octandionatocerium (III), cerium trifluoromethanesulfonate (III), 1,2,3,4-tetramethyl-2,4-cyclopentadienylcerium (III) can do.

式（８）中、Ｒ^１７は、炭素数１～２０の炭化水素基を表し、２つ以上のＲ^１７は、互いに結合して環を形成していてもよい。 Further, as the trivalent cerium salt, a silazane anion-coordinated cerium compound represented by the following formula (8) can be used.

In the formula (8), R ¹⁷ represents a hydrocarbon group having 1 to 20 carbon atoms, and two or more R ¹⁷ may be bonded to each other to form a ring.

Specific examples of R ¹⁷ include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert. -Amil, cyclopentyl, n-hexyl, cyclohexyl, methylcyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecil, n-eicocil; cyclobutenyl, cyclopentadienyl, cyclohexenyl, cyclooctenyl, cyclooctadienyl, 1-adamantyl; phenyl, toluyl, xylenyl , Ethylphenyl, isopropylphenyl, butylphenyl, naphthyl, anthracenyl, benzyl, phenylethyl and the like.

^R17 is, among other things, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert. -Amil, cyclopentyl, n-hexyl, cyclohexyl, methylcyclohexyl, n-heptyl, cyclobutenyl, cyclopentadienyl, cyclohexenyl, phenyl, toluyl, etc. Linear or branched alkyl group with 7 or less carbon atoms, cyclic alkyl group , Cyclic aryl groups are preferred. Particularly preferred are methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert. -Alkyl group having 4 or less carbon atoms such as butyl.

Specific examples of the cerium anion-coordinating cerium compound of the above formula (8) include those represented by the following formulas 8-1 to 8-15. Of these, formulas 8-1 and 8-7 to 8-12 are preferable.

The trivalent cerium salt is preferably 2,4-pentandionatocerium (III), trifluoroacetylacetonatocerium (III), 6,6,7,7,8,8,8-heptafluoro-. 2,2-dimethyl-3,5-octanedionatocerium (III), cerium trifluoromethanesulfonate (III), 1,2,3,4-tetramethyl-2,4-cyclopentadienylcerium (III) , The cerium anion-coordinating cerium compound of the above formula (8). Particularly preferred is the cerium anion-coordinated cerium compound of the above formula (8).

The inert solvent that can be used as the reaction medium is not particularly limited, and for example, saturated hydrocarbons such as n-pentane, i-pentane, n-hexane, cyclohexane, n-heptane, and n-decane; toluene and xylene. , Decene-1, etc., unsaturated hydrocarbons; diethyl ether, dipropyl ether, tert. -Ethers such as butyl methyl ether, dibutyl ether, cyclopentyl methyl ether and tetrahydrofuran; methanol, ethanol, isopropanol, n-butanol, sec-butanol, tert. -Alcohols such as butanol, 2-ethylhexanol; nitriles such as acetonitrile, octanonitrile, decanonitrile, pentadecanonitrile; dimethyl sulfoxide, N, N-dimethylformamide, N, N, N', N'-tetramethylethylenediamine , Hexamethylphosphate triamide and the like; halogen-containing solvents such as chloroform, dichloromethane, tetrachloromethane, dichloroethane and the like. Moreover, these mixed solvents can also be used.

The reaction temperature for producing a cerium complex containing a trivalent cerium and a carbene compound is preferably in the range of -100 to 200 ° C, which is an industrially used temperature, and particularly preferably -85 to 150 ° C. It is a range. The pressure conditions for the reaction can be any of pressure, normal pressure, and reduced pressure.
Further, when reacting the trivalent cerium salt with the carbene compound, the amount of the carbene compound used is preferably 0.0001 mol to 1,000,000 mol, particularly preferably 0.001 mol to 1,000,000 mol, based on 1 mol of the cerium content in the trivalent cerium salt. Is in the range of 0.001 mol to 100,000 mol. If it is out of this range, the emission intensity may decrease, and the durability and emission life may decrease.

The cerium complex containing trivalent cerium and a carben compound obtained by the reaction in an inert solvent may be used as it is, or filtered using a glass filter, a sintered porous body or the like, sublimation, recrystallization, or silica. Purification can also be performed by using a purification means such as column separation using alumina or a polymer gel. At this time, the purification means may be used in combination of these means, if necessary.
The cerium complex composition of the present invention may be a cerium complex composition containing the above-mentioned inert solvent, a trivalent cerium salt, a compound such as a carbene compound, and the like.

Next, an imidazolidene carbene compound having a phosphinyl group, which is a preferable novel carbene compound in the production of the cerium complex of the present invention, will be described.
Examples of the imidazolidenylcarbene compound having a phosphinyl group include the above formulas 1-28 to 1-34, and among them, 1,3-represented by the above formula 1-28 (formula (5)). Bis (2- (diphenylphosphinyl) benzyl) imidazolidene, 1,3-bis (3- (diphenylphosphinyl) benzyl) imidazolidene represented by the above formula 1-33, the above formula 1-34. The indicated 1,3-bis (4- (diphenylphosphinyl) benzyl) imidazolidene is preferred. Particularly preferred is 1,3-bis (2- (diphenylphosphinyl) benzyl) imidazolidene represented by the above formula 1-28 and the above formula (5).

The imidazolium halide compound having a phosphinyl group can be produced by reacting an aromatic halide compound having a phosphinyl group with an imidazole compound.
Specific examples of the imidazolium halide compound having a phosphinyl group include compounds of the following formulas 9-1 to 9-34. X in formulas 9-1 to 9-34 is chlorine, bromine, or iodine, preferably chlorine or bromine, and particularly preferably bromine.

Examples of the aromatic halide compound having a phosphineyl group include (2- (chloromethyl) phenyl) diphenylphosphine oxide, (2- (bromomethyl) phenyl) diphenylphosphine oxide, (2- (iodomethyl) phenyl) diphenylphosphine oxide, and (3). -(Chloromethyl) phenyl) diphenylphosphine oxide, (3- (bromomethyl) phenyl) diphenylphosphine oxide, (3- (iodomethyl) phenyl) diphenylphosphine oxide, (4- (chloromethyl) phenyl) diphenylphosphine oxide, (4) -(Bromomethyl) phenyl) diphenylphosphine oxide, (4- (iodomethyl) phenyl) diphenylphosphine oxide, (2- (chloromethyl) phenyl) dinaphthylphosphine oxide, (2- (bromomethyl) phenyl) dinaphthylphosphine oxide, ( 2- (Iodomethyl) phenyl) dinaphthylphosphine oxide, (3- (chloromethyl) phenyl) dinaphthylphosphine oxide, (3- (bromomethyl) phenyl) dinaphthylphosphine oxide, (3- (iodomethyl) phenyl) dinaphthylphosphine Oxides, (4- (chloromethyl) phenyl) dinaphthylphosphine oxides, (4- (bromomethyl) phenyl) dinaphthylphosphine oxides, (4- (iodomethyl) phenyl) dinaphthylphosphine oxides, (2- (chloromethyl) phenyls) ) Diisopropylphosphine oxide, (2- (bromomethyl) phenyl) diisopropylphosphine oxide, (2- (iodomethyl) phenyl) diisopropylphosphine oxide, (3- (chloromethyl) phenyl) diisopropylphosphine oxide, (3- (bromomethyl) phenyl) Diisopropylphosphine oxide, (3- (iodomethyl) phenyl) diisopropylphosphine oxide, (4- (chloromethyl) phenyl) diisopropylphosphine oxide, (4- (bromomethyl) phenyl) diisopropylphosphine oxide, (4- (iodomethyl) phenyl) diisopropyl Phosphine oxide, (2- (chloromethyl) phenyl) ditert. -Butyl phosphine oxide, (2- (bromomethyl) phenyl) ditert. -Butyl phosphine oxide, (2- (iodomethyl) phenyl) ditert. -Butyl phosphine oxide, (3- (chloromethyl) phenyl) ditert. -Butyl phosphine oxide, (3- (bromomethyl) phenyl) ditert. -Butyl phosphine oxide, (3- (iodomethyl) phenyl) ditert. -Butyl phosphine oxide, (4- (chloromethyl) phenyl) ditert. -Butyl phosphine oxide, (4- (bromomethyl) phenyl) ditert. -Butyl phosphine oxide, (4- (iodomethyl) phenyl) ditert. -Butyl phosphine oxide, (2- (chloromethyl) phenyl) dicyclohexylphosphine oxide, (2- (bromomethyl) phenyl) dicyclohexylphosphine oxide, (2- (iodomethyl) phenyl) dicyclohexylphosphine oxide, (3- (chloromethyl) phenyl ) Dicyclohexylphosphine oxide, (3- (bromomethyl) phenyl) dicyclohexylphosphine oxide, (3- (iodomethyl) phenyl) dicyclohexylphosphine oxide, (4- (chloromethyl) phenyl) dicyclohexylphosphine oxide, (4- (bromomethyl) phenyl) Examples thereof include dicyclohexylphosphine oxide and (4- (iodomethyl) phenyl) dicyclohexylphosphine oxide.

Among the above aromatic halide compounds having a phosphinyl group, (2- (chloromethyl) phenyl) diphenylphosphine oxide, (2- (bromomethyl) phenyl) diphenylphosphine oxide, (3- (chloromethyl) phenyl) are preferable. Diphenylphosphine oxide, (3- (bromomethyl) phenyl) diphenylphosphine oxide, (4- (chloromethyl) phenyl) diphenylphosphine oxide, (4- (bromomethyl) phenyl) diphenylphosphine oxide, (2- (chloromethyl) phenyl) Dinaphthylphosphine oxides, (2- (bromomethyl) phenyl) dinaphthylphosphine oxides, (3- (chloromethyl) phenyl) dinaphthylphosphine oxides, (3- (bromomethyl) phenyl) dinaphthylphosphine oxides, (4- (chloro) Methyl) phenyl) dinaphthylphosphine oxide, (4- (bromomethyl) phenyl) dinaphthylphosphine oxide, (2- (chloromethyl) phenyl) diisopropylphosphine oxide, (2- (bromomethyl) phenyl) diisopropylphosphine oxide, (3-) (Chloromethyl) phenyl) diisopropylphosphine oxide, (3- (bromomethyl) phenyl) diisopropylphosphine oxide, (4- (chloromethyl) phenyl) diisopropylphosphine oxide, (4- (bromomethyl) phenyl) diisopropylphosphine oxide, (2-) (Chloromethyl) phenyl) ditert. -Butyl phosphine oxide, (2- (bromomethyl) phenyl) ditert. -Butyl phosphine oxide, (3- (chloromethyl) phenyl) ditert. -Butyl phosphine oxide, (3- (bromomethyl) phenyl) ditert. -Butyl phosphine oxide, (4- (chloromethyl) phenyl) ditert. -Butyl phosphine oxide, (4- (bromomethyl) phenyl) ditert. -Butyl phosphine oxide, (2- (chloromethyl) phenyl) dicyclohexylphosphine oxide, (2- (bromomethyl) phenyl) dicyclohexylphosphine oxide, (3- (chloromethyl) phenyl) dicyclohexylphosphine oxide, (3- (bromomethyl) phenyl) ) Dicyclohexylphosphine oxide, (4- (chloromethyl) phenyl) dicyclohexylphosphine oxide, (4- (bromomethyl) phenyl) dicyclohexylphosphine oxide.

Of these, (2- (bromomethyl) phenyl) diphenylphosphine oxide, (3- (bromomethyl) phenyl) diphenylphosphine oxide, (4- (bromomethyl) phenyl) diphenylphosphine oxide, and (2- (bromomethyl) phenyl) are particularly preferable. ) Dinaphthylphosphine oxide, (3- (bromomethyl) phenyl) dinaphthylphosphine oxide, (4- (bromomethyl) phenyl) dinaphthylphosphine oxide, (2- (bromomethyl) phenyl) diisopropylphosphine oxide, (3- (bromomethyl)) Phosphine) diisopropylphosphine oxide, (4- (bromomethyl) phenyl) diisopropylphosphine oxide, (2- (bromomethyl) phenyl) ditert. -Butyl phosphine oxide, (3- (bromomethyl) phenyl) ditert. -Butyl phosphine oxide, (4- (bromomethyl) phenyl) ditert. -Butyl phosphine oxide, (2- (bromomethyl) phenyl) dicyclohexylphosphine oxide, (3- (bromomethyl) phenyl) dicyclohexylphosphine oxide, (4- (bromomethyl) phenyl) dicyclohexylphosphine oxide.

On the other hand, examples of the imidazole compound include imidazole, benzimidazole, 5,6-dimethylbenzimidazole, 5-tert. -Butylbenzimidazole, hexahydrobenzimidazole and the like can be mentioned. Among them, imidazole, benzimidazole, 5,6-dimethylbenzimidazole and the like are preferable, and imidazole, benzimidazole and the like are particularly preferable.

The reaction conditions between the aromatic halide compound having a phosphinyl group and the imidazole compound are not particularly limited, but the aromatic halide compound having a phosphinyl group is added to 1 mol of imidazole in the above-mentioned inert solvent. It is preferable to react with a quantitative ratio of 2.0 mol or more. The reaction temperature is preferably in the range of −100 to 200 ° C., which is an industrially used temperature, and particularly preferably in the range of −85 to 150 ° C. The pressure conditions for the reaction can be any of pressure, normal pressure, and reduced pressure.

The imidazolium halide compound having a phosphinyl group represented by the example of the following formula (9), which is produced as described above, has a phosphinyl group by desorbing hydrogen halide under basic conditions or the like. It can be an imidazolidenecarbene compound having. The desorption reaction of this hydrogen halide may be carried out in advance before the preparation of the cerium complex, or may be carried out during the preparation of the cerium complex. As the reaction conditions, the same conditions as those of the above-mentioned reaction conditions of the aromatic halide compound having a phosphinyl group and the imidazole compound can be used.
Examples of the base that can be used above include lithium compounds such as butyl lithium and lithium bis (trimethylsilyl) amide, and sodium compounds such as sodium hydrogen carbonate, sodium hydroxide and sodium methoxy.

Examples are shown below, but the present invention is not limited to these examples.
The fluorescence emission measurement was performed using an F-4500 fluorescence spectrophotometer manufactured by Hitachi High-Technologies Corporation.

Example 1
[Synthesis of imidazolium halide compound]
In a 50 mL three-necked flask equipped with a reflux condenser and a stirrer, 0.32 g (13 mmol) of metallic magnesium powder and 3.3 mg (0.013 mmol) of iodine were charged under an argon stream and stirred for 8 hours. Then, a solution prepared by dissolving 1.9 g (11 mmol) of 2-bromotoluene in 10 ml of tetrahydrofuran (THF) was added dropwise from a dropping filter. After completion of the dropping, the mixture was stirred under THF reflux for 3 hours.
The obtained THF solution of 2-toluyl magnesium bromide was cooled to −78 ° C., a solution prepared by dissolving 3.3 g (15 mmol) of chlorodiphenylphosphine in 2 ml of THF was added, the temperature was raised to room temperature, and the mixture was stirred for 8 hours. ..

The chloromagnesium bromide precipitated from the obtained reaction mixture was filtered off by a glass filter and washed with 5 ml of pure water and 5 ml of saturated brine. The crude diphenyl (2-toluyl) phosphine solution was dried over magnesium sulfate, THF was distilled off, and the mixture was vacuum dried to obtain a yellow oily crude diphenyl (2-toluyl) phosphine. The obtained crude diphenyl (2-toluyl) phosphine was purified by flash silica gel chromatography (ethyl acetate / n-hexane) to obtain 0.88 g (3.2 mmol) of diphenyl (2-toluyl) phosphine.

A solution prepared by dissolving 0.86 g (3.1 mmol) of this diphenyl (2-toluyl) phosphine in 5 ml of chloroform was placed in a 30 mL eggplant flask equipped with a stirrer, cooled in an ice bath, and 34. 6.1 g (62 mmol) of 5% hydrogen peroxide solution was added dropwise, and the mixture was stirred for 40 minutes. After separating the organic layer with a liquid separation filter, the aqueous layer was washed 5 times with 5 ml of chloroform. The obtained organic layer was dried over magnesium sulfate, chloroform was distilled off, and the mixture was vacuum dried to obtain a yellow solid crude diphenyl (2-toluyl) phosphine oxide. The obtained crude diphenyl (2-toluyl) phosphine oxide was dissolved in ethyl acetate / n-hexane and recrystallized to obtain 0.91 g (3.1 mmol) of a white solid of diphenyl (2-toluyl) phosphine oxide. rice field.

0.91 g (3.1 mmol) of this diphenyl (2-toluyl) phosphine oxide white solid, 20 ml of carbon tetrachloride, 0.56 g (3.2 mmol) of N-bromosuccinimide, and 0.051 g of azobisisobutyronitrile (0.051 g). 0.31 mmol) was placed in a 50 mL three-necked flask equipped with a reflux condenser and a stirrer under an argon stream, and the mixture was stirred under reflux of carbon tetrachloride for 4 hours. The obtained reaction mixture was washed 3 times with 20 ml of pure water and once with 20 ml of saturated brine. The obtained organic layer was dried over magnesium sulfate, carbon tetrachloride was distilled off, and the mixture was vacuum dried to obtain crude 2-diphenylphosphinyl-benzyl bromide as a black-orange oil. This was purified by flash silica gel chromatography (ethyl acetate / n-hexane) to obtain 0.50 g (1.3 mmol) of 2-diphenylphosphinyl-benzyl bromide.

0.054 g (0.15 mmol) of o-diphenylphosphinyl-benzyl bromide, 0.0050 g (0.073 mmol) of imidazole, 0.0070 g (0.0083 mmol) of sodium hydrogen carbonate, and 1.0 ml of THF are added to a reflux condenser. And a 20 ml Schlenk tube equipped with a stirrer was charged, and the mixture was stirred under reflux at THF for 3 hours. The obtained reaction mixture was extracted 3 times with 10 ml of chloroform using a separate filter, and washed once with 10 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, the solvent was distilled off, and the mixture was vacuum dried to obtain a yellow oily crude 1,3-bis (2- (diphenylphosphinyl) benzyl) imidazolium bromide. .. This was dissolved in chloroform / n-hexane and recrystallized to obtain 0.016 g (0.022 mmol) of a yellow solid of 1,3-bis (2- (diphenylphosphinyl) benzyl) imidazolium bromide. .. The results of analyzing this with ¹ HNM R were as follows.
¹ HNM R (CDCl ₃ , 300 MHz); δ5.73 ppm (s, 4H), δ7.01 ppm (m, 2H), δ7.32 ppm (m, 2H), δ7.45-7.67 ppm (m, 22H), 7.91ppm (d, J = 1.5Hz, 2H), 8.13 (m, 2H), 11.26ppm (s, 1H)

Example 2
[In that case of carbene compound, preparation of cerium complex containing trivalent cerium and carbene compound (1-28) of formula (5)]
A 20 ml Schlenk tube is mixed with 5 ml of toluene, 99 mg (0.40 mmol) of cerium trichloride, and 5.0 ml (6.5 mmol) of a 1.3 mol / L-THF solution of lithium bis (trimethylsilyl) amide, and trivalent cerium. A solution (cerium concentration 0.040 mmol / ml) was used.
1.0 ml (0.040 mmol) of this trivalent cerium solution and 192 mg (0.26 mmol) of 1,3-bis (2- (diphenylphosphinyl) benzyl) imidazolium bromide synthesized in Example 1 were added to 20 ml of Schlenk. It was charged into a tube and stirred to obtain a cerium complex containing trivalent cerium and the carbene compound (1-28) of the formula (5). When excited with excitation light of λ _ex = 365 nm and the fluorescence spectrum was measured, an emission spectrum having a peak of λ _em = 537 nm and a half width = Δ213 nm was obtained.

Example 3
[Synthesis of imidazolium halide compound]
In a 100 mL three-necked flask equipped with a stirrer, 3,5-di-tert. -2.0 g (8.5 mmol) of butyl salicylaldehyde, 28 ml of ethanol, and 0.18 g (4.8 mmol) of sodium borohydride were charged under an argon stream and stirred at room temperature for 30 minutes. After distilling off ethanol, pure water was added, the pH was further adjusted to 2 with acetic acid, and the mixture was extracted with ethyl acetate. The obtained organic layer was dried over sodium sulfate, ethyl acetate was distilled off, and the mixture was vacuum dried to obtain crude 2,4-di-tert. -Butyl-6-hydroxymethylphenol was obtained. This was dissolved in hexane, recrystallized and purified, and 2,4-di-tert. 1.2 g (5.1 mmol) of white needle-like crystals of -butyl-6-hydroxymethylphenol was obtained.

This 2,4-di-tert. 0.73 g (3.1 mmol) of -butyl-6-hydroxymethylphenol and 3 ml of toluene were placed in a 35 ml Schlenk tube equipped with a stirrer, 0.56 g (4.7 mmol) of thionyl chloride was added, and the mixture was added at room temperature for 45 minutes. Stirred. Toluene was distilled off and dried in vacuum to obtain 2,4-di-tert. 0.78 g (3.1 mmol) of a white solid of -butyl-6-chloromethylphenol was obtained.
On the other hand, 0.017 g (0.25 mmol) of imidazole, 0.021 g (0.25 mmol) of sodium hydrogen carbonate and 1.0 ml of THF were charged into a 20 ml Schlenk tube equipped with a reflux condenser and a stirrer, and then obtained as described above. 2,4-Di-tert. A solution prepared by dissolving 0.14 g (0.55 mmol) of -butyl-6-chloromethylphenol in 0.6 ml of THF was added, and the mixture was stirred under reflux for 90 minutes. The obtained reaction mixture was extracted 3 times with 10 ml of chloroform using a separate filter, and washed once with 10 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, the solvent was distilled off, and the mixture was vacuum dried to make a yellow solid crude 1,3-bis (3,5-di-tert.-butyl-2-hydroxybenzyl). Obtained imidazolium chloride. This is suspended in diethyl ether, filtered through a glass filter, washed 3 times with diethyl ether, and then vacuum dried to 1,3-bis (3,5-di-tert.-butyl-2-hydroxybenzyl) imidazo. 0.085 g (0.16 mmol) of a white solid of rium chloride was obtained. The results of analyzing this with ¹ HNM R were as follows.
¹ HNM R (CDCl ₃ , 300 MHz); δ1.27 ppm (s, 18H), δ1.39 ppm (s, 18H), δ5.53 ppm (s, 4H), 7.06 ppm (d, J = 2. 4Hz, 2H), δ7.09ppm (s, 2H), 7.36ppm (d, J = 2.4Hz, 2H), δ7.76ppm (s, 2H), δ9.51ppm (s, 1H)

Example 4
[The case of carbene compound, preparation of cerium complex containing trivalent cerium and carbene compound (1-26) of formula (4)]
In Example 1, 1,3-bis (3,5-) synthesized in Example 3 was changed to 192 mg (0.26 mmol) of 1,3-bis (2- (diphenylphosphinyl) benzyl) imidazolium bromide. Di-tert.-Butyl-2-hydroxybenzyl) Imidazole chloride 130 mg (0.24 mmol) was carried out in the same manner as in Example 1 to obtain trivalent cerium and the formula (4) carbene compound (4). A cerium complex containing 1-26) was prepared. As a result of measuring the fluorescence spectrum, the emission spectrum had a peak wavelength λ _em = 481 nm and a half width = Δ129 nm.

Example 5
[In that case of carbene compound, preparation of cerium complex containing trivalent cerium and carbene compound (1-10) of formula (3)]
In Example 1, 192 mg (0.26 mmol) of 1,3-bis (2- (diphenylphosphinyl) benzyl) imidazolium bromide was changed to 1,1 of the raw material of the carbene compound (1-10) of the formula (3). An imidazolium halide compound was obtained by carrying out in the same manner as in Example 1 except that 3-dimesityl imidazolium chloride was adjusted to 82 mg (0.24 mmol). By reacting this imidazolium halide compound in the same manner as in Example 2, a cerium complex containing trivalent cerium and the carbene compound (1-10) of the formula (3) was prepared. As a result of measuring the fluorescence spectrum of this, the emission spectrum had a peak wavelength of λ _em = 466 nm and a half width of Δ177 nm.

Comparative Example 1
In Example 2, the carbene compound is not contained in the same manner as in Example 1 except that lithium bis (trimethylsilyl) amide and 1,3-bis (2- (diphenylphosphinyl) benzyl) imidazolium bromide were not added. A cerium complex was prepared. The fluorescence spectrum was measured, but no light emission was observed in the visible light region, which was visually observable.

The cerium complex of the present invention can be used in a wide range of fields as a phosphor for LEDs, an organic EL light emitting layer material, a wavelength conversion material for a solar cell device, a wavelength conversion film for agricultural facilities, and a photosensitizer for a photocatalyst for a redox reaction.

Claims (13)

A cerium complex containing trivalent cerium and a carbene compound represented by the following formula (1).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are hydrogen atoms, hydroxy groups, carboxyl groups, phosphonic acid groups, and phosphine oxides . It represents a group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group containing an oxygen atom or a phosphorus atom, and they may be bonded to each other to form a ring. R ¹¹ and R ¹² are hydrogen. An atom represents a hydrocarbon group having 1 to 20 carbon atoms, which may be bonded to each other to form a ring. X represents an integer of 0 to 10). The cerium complex according to claim 1, which is represented by the following formula (2).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and x are the definitions in formula (1). The same. N represents an integer of 1 or more. L represents an anion of halogen, silazane, sulfonic acid or β-diketone.) R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, hydroxy groups, or phosphine oxide groups. , The cerium complex according to claim 1 or 2. The cerium complex according to any one of claims 1 to 3, wherein the carbene compound is an imidazolidene carbene compound having a phosphinyl group. The cerium complex according to claim 4, wherein the imidazolidene carbene compound having a phosphinyl group is a compound represented by the following formula (5).

The cerium complex according to any one of claims 1 to 3, wherein the carbene compound is a compound represented by the following formula (3) or formula (4).

A cerium complex composition comprising the cerium complex according to any one of claims 1 to 6. A light emitting material containing the cerium complex according to any one of claims 1 to 6. A light emitting material containing the cerium complex composition according to claim 7. The light emitting material according to claim 8 or 9, which is excited by ultraviolet light or visible light and emits blue light. A sensitizer for an LED device, an organic EL device, a solar cell device, a film for an agricultural facility, or a photocatalyst for a redox reaction, which comprises the light emitting material according to claim 8 or 9. An imidazolium halide compound which is 1,3-bis (2- (diphenylphosphinyl) benzyl) imidazolium bromide. An imidazolidene carbene compound which is 1,3-bis (2- (diphenylphosphinyl) benzyl) imidazolidene represented by the following formula (5).