WO2015053291A1 - Light-emitting material including platinum complex - Google Patents
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- WO2015053291A1 WO2015053291A1 PCT/JP2014/076861 JP2014076861W WO2015053291A1 WO 2015053291 A1 WO2015053291 A1 WO 2015053291A1 JP 2014076861 W JP2014076861 W JP 2014076861W WO 2015053291 A1 WO2015053291 A1 WO 2015053291A1
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- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
Definitions
- the present invention relates to a light emitting material containing a platinum complex and the platinum complex.
- the phosphorescent light emission by the organometallic complex can achieve a theoretically higher quantum efficiency than the fluorescent light emission in organic EL (electroluminescence).
- the said organometallic complex is anticipated as a material of functional elements, such as an organic light emitting element which is a next generation technique, specifically, a material of an organic EL display, etc.
- organic platinum complexes have been attracting attention as phosphorescent materials as organometallic complexes.
- an organic platinum complex containing a platinum atom coordinated with two NN type bidentate ligands or two NO type bidentate ligands is known (for example, Patent Document 1).
- An organic platinum complex containing a platinum atom coordinated by a tetradentate ligand is also known (for example, Patent Document 2).
- platinum complex A coordinated by ppy (phenylpyridine) and acac (acetylacetonate)
- Patent Document 3 Non-Patent Document 1
- platinum complexes have been reported to emit light in solution or in a low concentration dispersion state.
- these platinum complexes are molecules with high planarity, they emit light in a high density state like crystals. The strength is considered weak.
- an organic platinum complex containing a platinum atom coordinated by two NO-type bidentate ligands connected by a bridge exhibits phosphorescence in a high-density state like a crystal (for example, Patent Document 4).
- an organic platinum complex containing a platinum atom coordinated with two asymmetrical NO-type bidentate ligands exhibits phosphorescence in a high-density state like a crystal (for example, Patent Document 5).
- an object of the present invention is to provide a light emitting material that is solid and has high emission intensity.
- the present invention is a light emitting material containing a platinum complex represented by the formula (I).
- Ar1 is a formula represented by any of the following formulas (i) to (xvii):
- Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, or one carbon atom.
- ⁇ 12 alkoxy group —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C ( ⁇ O) O— (alkyl group having 1 to 6 carbon atoms), phenyl Group, phenoxy group, nitrile group, nitro group, or thiol group.
- the substituent R1 in the formulas represented by the formulas (i) to (xiii) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (i) to (xiii). In the case of having two or more substituents R1, the substituents R1 may be different or the same.
- the substituent R2 in the formulas represented by the formulas (xx) to (xxv) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xx) to (xxv). When it has two or more substituents R2, the substituents R2 may be different or the same.
- the present invention is a platinum complex represented by the formula (X).
- Ar2 is a formula represented by any of the following formulas (xxxi) to (xxxvii):
- Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
- R3 is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, —NH 2 , —N (carbon An alkyl group having a number of 1 to 6) 2 , —OH, —COOH, —C ( ⁇ O) O— (an alkyl group having 1 to 6 carbon atoms), a phenyl group, a phenoxy group, a nitrile group, a nitro group, or a thiol group
- R2 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, or an alkoxy having 1 to 12 carbon atoms.
- the substituent R4 in the formulas represented by the formulas (xxxii) to (xxxiii) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xxxii) to (xxxiii). When it has two or more substituents R4, the substituents R4 may be different or the same.
- the substituent R2 in the formulas represented by the formulas (xx) to (xxv) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xx) to (xxv). When it has two or more substituents R2, the substituents R2 may be different or the same.
- the light emitting material containing the platinum complex of the present invention is solid and has an advantage of high emission intensity.
- FIG. 1 is an X-ray crystal structure diagram of the compound (1) of Example 1.
- FIG. 2 is an X-ray crystal structure diagram of the compound (3) of Example 3.
- FIG. 3 is an X-ray crystal structure diagram of the compound (4) of Example 4.
- FIG. 4 is an X-ray crystal structure diagram of the compound (6) of Example 6.
- FIG. 5 is a packing diagram in the crystal of the compound (3) of Example 3.
- the present inventors expect that, when bis (iminophenoxy) platinum is used as a mother skeleton and a bulky aromatic ring group is substituted for an imino nitrogen atom, strong emission intensity is exhibited in a high-density solid state such as a crystal. I found it outside. Specifically, in the following formula (I), it was found that if Ar1 is an aromatic ring group, the molecule has a non- ⁇ stack type structure in the crystal, and as a result, the emission intensity increases. On the other hand, it has also been found that in the following formula (I), when Ar is a chain alkyl group, the emission intensity does not increase in the crystal. Based on these findings, the present inventors have completed the present invention.
- “solid” means crystal, glass or the like.
- the light emitting material containing the platinum complex of the present invention is solid and preferably has high emission intensity at room temperature.
- the platinum complex in the luminescent material of the present invention is represented by the following formula (I).
- Ar1 is a formula represented by any of the following formulas (i) to (xvii):
- Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, or one carbon atom.
- ⁇ 12 alkoxy group —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C ( ⁇ O) O— (alkyl group having 1 to 6 carbon atoms), phenyl Group, phenoxy group, nitrile group, nitro group, or thiol group, preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or —N (an alkyl group having 1 to 6 carbon atoms) 2 And more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a halogen atom.
- the substituent R1 in the formulas represented by the formulas (i) to (xiii) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (i) to (xiii). , 1 to 2 hydrogen atoms in the formulas represented by formulas (i) to (xiii) may be substituted. In the case of having two or more substituents R1, the substituents R1 may be different or the same.
- the substituent R2 in the formulas represented by the formulas (xx) to (xxv) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xx) to (xxv), For example, one or two hydrogen atoms in the formulas represented by formulas (xx) to (xxv) may be substituted. When it has two or more substituents R2, the substituents R2 may be different or the same.
- alkyl group having 1 to 12 carbon atoms includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like.
- the alkyl group may be linear or branched.
- the alkyl group having 1 to 12 carbon atoms is, for example, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.
- C2-C12 alkenyl group includes, for example, ethylenyl, propylenyl, butenyl, pentenyl, hexenyl and the like.
- the alkenyl group may be linear or branched.
- Examples of the alkenyl group having 2 to 12 carbon atoms include alkenyl groups having 2 to 10 carbon atoms, preferably 5 to 10 carbon atoms, and more preferably 5 to 8 carbon atoms.
- alkynyl group having 2 to 12 carbon atoms includes, for example, acetylenyl, propenyl and the like.
- the alkynyl group may be linear or branched.
- the alkynyl group having 2 to 12 carbon atoms is, for example, an alkynyl group having 2 to 10 carbon atoms, preferably 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms.
- alkoxy group having 1 to 12 carbon atoms is an alkyloxy group.
- the alkyl part of the alkyloxy group is the same as the alkyl group having 1 to 12 carbon atoms.
- Examples of the alkoxyl group include methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy and the like.
- the alkoxy group having 1 to 12 carbon atoms is, for example, an alkoxy group having 1 to 10 carbon atoms, preferably 5 to 10 carbon atoms, and more preferably 5 to 8 carbon atoms.
- the alkyl group moiety of the term “—N (C 1-6 alkyl group) 2 ” is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl and the like.
- the alkyl moieties may be the same as or different from each other.
- Examples of —N (C 1-6 alkyl group) 2 include dimethylamino, diethylamino, methylethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino and the like.
- the alkyl group moiety may be linear or branched.
- —N (alkyl group having 1 to 6 carbon atoms) 2 is, for example, —N (alkyl group having 1 to 5 carbon atoms) 2 , preferably —N (alkyl group having 1 to 4 carbon atoms) 2 , more preferably Is —N (an alkyl group having 1 to 3 carbon atoms) 2 .
- the alkyl group moiety of the term “—C ( ⁇ O) O— (C 1-6 alkyl group)” is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl and the like.
- Examples of —C ( ⁇ O) O— (an alkyl group having 1 to 6 carbon atoms) include —C ( ⁇ O) O-methyl, —C ( ⁇ O) O-ethyl, —C ( ⁇ O) O.
- Examples of —C ( ⁇ O) O— include —C ( ⁇ O) O— (alkyl group having 1 to 5 carbon atoms), preferably —C ( ⁇ O).
- O— an alkyl group having 1 to 4 carbon atoms
- more preferably —C ( ⁇ O) O— an alkyl group having 1 to 3 carbon atoms.
- Ar1 is a formula represented by the formula (i), the formula (ii), the formula (iii), the formula (iv), or the formula (v).
- Ring X is a formula represented by the formula (xx), the formula (xxi) or the formula (xxii) together with the carbon atoms a and b.
- R1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2 ; R1 in formula (i) is replaced with one or two hydrogen atoms in the formula represented by formula (i); In the case of having two R1s in formula (i), the two R1s may be the same or different from each other, R1 in formula (ii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (ii); In the case of having two R1s in formula (ii), the two R1s may be the same or different from each other, R1 in formula (iii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (iii); In the case of having two R1s in formula (iii), the two R1s may be the same or different from each other, R1 in formula (iv) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (iv);
- Ar1 is a formula represented by Formula (i) or (ii)
- Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
- R1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
- R1 in formula (i) is replaced with one or two hydrogen atoms in the formula represented by formula (i);
- the two R1s may be the same or different from each other, R1 in formula (ii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (ii);
- R2 is more preferably a platinum complex of the formula (I) which is a hydrogen atom.
- Ar1 is a formula represented by Formula (i) or (ii)
- Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
- R1 is a hydrogen atom, a halogen atom or an alkyl group having 1 to 12 carbon atoms, R1 in formula (i) is replaced with one or two hydrogen atoms in the formula represented by formula (i);
- R1 in formula (ii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (ii);
- R2 is more preferably a platinum complex of the formula (I) which is a hydrogen atom. This is because such a platinum complex has high emission intensity at room temperature.
- the platinum complex in the light emitting material of the present invention is preferably a compound represented by the following formula, for example.
- the compounds represented by the formulas (2), (3), (4), (5), (6), (7) and (8) because the emission intensity is not significantly reduced by temperature change. are more preferred, and compounds of formulas (3) and (6) are more preferred.
- the platinum complex of the present invention is represented by the following formula (X).
- Ar2 is a formula represented by any of the following formulas (xxxi) to (xxxvii):
- Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
- R3 is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, —NH 2 , —N (carbon An alkyl group having a number of 1 to 6) 2 , —OH, —COOH, —C ( ⁇ O) O— (an alkyl group having 1 to 6 carbon atoms), a phenyl group, a phenoxy group, a nitrile group, a nitro group, or a thiol group
- it is an alkyl group having 1 to 12 carbon atoms, a halogen atom or —N (an alkyl group having 1 to 6 carbon atoms) 2 , more preferably an alkyl group having 1 to 12 carbon atoms or a halogen atom.
- R2 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, or an alkoxy having 1 to 12 carbon atoms.
- substituent R3 in the formula represented by the formula (xxxi) may be replaced with one or more hydrogen atoms in the formula represented by the formula (xxxi), for example, represented by the formula (xxxi). It may be replaced with 1 to 2 hydrogen atoms in the formula. When it has two or more substituents R3, the substituents R3 may be different or the same.
- the substituent R4 in the formulas represented by the formulas (xxxii) to (xxxiii) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xxxii) to (xxxiii), For example, it may be replaced with 1 to 2 hydrogen atoms in the formulas represented by the formulas (xxxii) to (xxxiii). In the case of having two or more substituents R1, the substituents R1 may be different or the same.
- the substituent R2 in the formulas represented by the formulas (xx) to (xxv) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xx) to (xxv), For example, one or two hydrogen atoms in the formulas represented by formulas (xx) to (xxv) may be substituted. When it has two or more substituents R2, the substituents R2 may be different or the same.
- Ar1 is a formula represented by the formula (xxxi), the formula (xxxii), the formula (xxxiii), the formula (xxxiv), or the formula (xxxv).
- Ring X is a formula represented by the formula (xx), the formula (xxi) or the formula (xxii) together with the carbon atoms a and b.
- R3 is a halogen atom, an alkyl group having 1 to 12 carbon atoms, or —N (an alkyl group having 1 to 6 carbon atoms) 2 ; R3 in formula (xxxi) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxi); In the case of having two R3 in the formula (xxxi), the two R3 may be the same or different from each other, R4 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2 ; R4 in formula (xxxii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxii); In the case of having two R4s in the formula (xxxii), the two R4s may be the same or different from each other, R4 in formula (xxxii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxi
- Ar2 is a formula represented by the formula (xxxi) or (xxxii)
- Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
- R3 is an alkyl group having 1 to 12 carbon atoms, a halogen atom or —N (an alkyl group having 1 to 6 carbon atoms) 2
- R4 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2
- R3 in formula (xxxi) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxi);
- the two R3 may be the same or different from each other, R4 in formula (xxxii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxii);
- R4s is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxii);
- Ar2 is a formula represented by the formula (xxxi) or (xxxii)
- Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
- R3 is an alkyl group having 1 to 12 carbon atoms or a halogen atom
- R4 is a hydrogen atom, a halogen atom or an alkyl group having 1 to 12 carbon atoms
- R3 in formula (xxxi) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxi);
- the two R3 may be the same or different from each other
- R4 in formula (xxxii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxii);
- the two R4s may be the same or different from each other, R2 is more preferably a platinum complex of the formula (X) which is
- the platinum complex of the light emitting material of the present invention can be produced, for example, as follows.
- a compound of formula (I) is reacted with a platinum compound in the presence of a base to give a compound of formula (I).
- platinum compound examples include PtCl 2 (CH 3 CN) 2 and K 2 PtCl 4 .
- the base for example, K 2 CO 3 , NaH, triethylamine or the like may be used. This reaction is carried out, for example, at 20 to 130 ° C. for 1 to 48 hours.
- the solvent for this reaction include, but are not limited to, a mixture of dimethylformamide (DMF) and methanol, dimethyl sulfoxide (DMSO), and the like.
- the compound represented by the formula (II) may be obtained commercially, or may be made in-house with reference to known literature.
- the compound represented by the formula (II) can be produced, for example, as follows.
- a compound of formula (II) is obtained by heating a salicylaldehyde derivative of formula (III) and 1 equivalent of an amine (compound of formula (IV)) in a solvent. This reaction is carried out, for example, at 20 to 100 ° C. for the necessary time.
- the solvent for this reaction include, but are not limited to, methanol, a mixture of dimethylformamide (DMF) and methanol, dimethyl sulfoxide (DMSO), and the like.
- the platinum complex represented by the formula (X) of the present invention can be produced in the same manner as the platinum complex represented by the formula (I).
- the light-emitting material of the present invention can be used as a high-luminance light-emitting material and a light-emitting material of an organic EL element, specifically, a material of a light-emitting layer.
- an organic EL element for example, a substrate, an anode, a hole transport layer, a light emitting layer containing the light emitting material of the present invention, an electron transport layer, and a cathode are laminated in this order.
- the substrate, the anode, the hole transport layer, the electron transport layer, and the cathode may be formed by a conventionally known manufacturing method using a conventionally known material.
- the light emitting layer may contain a host material in addition to the light emitting material of the present invention.
- the host material include those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an arylsilane skeleton.
- the quantum yield was measured using a fluorometer FP-6500N, a low-temperature medium integrating sphere system INK-533 for phosphorescence measurement, and a liquid sample cell LPH-120 (all manufactured by JASCO Corporation).
- Example 1 the crystal structure of the compound (3) in Example 3 is shown in FIG. 2, and the crystal structure of the compound (4) in Example 4 is shown in FIG.
- the crystal structure of the compound (6) of Example 6 is shown in FIG.
- crystallization of the compound (3) of Example 3 obtained as a result of the crystal analysis is shown in FIG.
- the platinum complex of the example had a structure in which Ar groups were fixed in the vertical direction with respect to the plane of the biiminoplatinum complex in the crystal. Further, as shown in FIG. 5, it was confirmed that the platinum complex of the example had a structure in which the molecules were not stacked in the crystal.
- the compound represented by the formula (I) has a structure in which an Ar group is fixed in the vertical direction with respect to the plane of the bisiminoplatinum complex in the crystal. Furthermore, in the compound represented by the formula (I), the arrangement of molecules in the crystal has a non- ⁇ stack structure. As a result, since the compound represented by the formula (I) does not quench between molecules in a crystalline state, it is considered that strong intensity phosphorescence can be realized.
- the light emitting material of the present invention is solid and has excellent light emission efficiency, it is possible to obtain light emission intensity sufficient for practical use. Therefore, the light-emitting material of the present invention is useful as a material for organic light-emitting elements that are the next generation technology.
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Abstract
The purpose of the present invention is to provide a light-emitting material that is a solid and has a high light-emission intensity. The light-emitting material includes a platinum complex indicated by formula (I). In the formula, Ar1 is a formula indicated by one among (i)-(xvii) and ring X combines with carbon atoms a and b and is a formula indicated by one among (xx)-(xxvi).
Description
本発明は、白金錯体を含む発光材料、および、その白金錯体に関する。
The present invention relates to a light emitting material containing a platinum complex and the platinum complex.
有機金属錯体による燐光性の発光は、有機ＥＬ（エレクトロルミネッセンス）において蛍光性の発光よりも理論的に高い量子効率を達成することが可能である。このため、当該有機金属錯体は、例えば次世代技術である有機発光素子等の機能素子の材料、具体的には有機ＥＬディスプレイの材料等として期待されている。
The phosphorescent light emission by the organometallic complex can achieve a theoretically higher quantum efficiency than the fluorescent light emission in organic EL (electroluminescence). For this reason, the said organometallic complex is anticipated as a material of functional elements, such as an organic light emitting element which is a next generation technique, specifically, a material of an organic EL display, etc.
また、紫外光励起により強い固体発光（結晶発光）を示すＰＬ（フォトルミネッセンス）化合物は、将来の機能性材料の観点からその開発が期待されている。
In addition, the development of PL (photoluminescence) compounds that exhibit strong solid-state light emission (crystal light emission) upon excitation with ultraviolet light is expected from the viewpoint of functional materials in the future.
近年、有機金属錯体として有機白金錯体が燐光発光材料として着目されてきている。例えば、２個のＮＮ型二座配位子または２個のＮＯ型二座配位子が配位した白金原子を含む有機白金錯体が知られている（例えば、特許文献１）。また、四座配位子が配位した白金原子を含む有機白金錯体も知られている（例えば、特許文献２）。
In recent years, organic platinum complexes have been attracting attention as phosphorescent materials as organometallic complexes. For example, an organic platinum complex containing a platinum atom coordinated with two NN type bidentate ligands or two NO type bidentate ligands is known (for example, Patent Document 1). An organic platinum complex containing a platinum atom coordinated by a tetradentate ligand is also known (for example, Patent Document 2).
また、白金に２種類の配位子を有する非対称型錯体として、たとえば、ppy(フェニルピリジン)、acac(アセチルアセトナート)が配位した白金錯体Ａ（特許文献３、非特許文献１）が知られている。これらの白金錯体は、溶液や低濃度分散状態で発光することが報告されているが、しかし、これらの白金錯体は、平面性の高い分子であることから、結晶のような高密度状態では発光強度は弱いと考えられる。
Further, as an asymmetric complex having two kinds of ligands in platinum, for example, platinum complex A coordinated by ppy (phenylpyridine) and acac (acetylacetonate) (Patent Document 3, Non-Patent Document 1) is known. It has been. These platinum complexes have been reported to emit light in solution or in a low concentration dispersion state. However, since these platinum complexes are molecules with high planarity, they emit light in a high density state like crystals. The strength is considered weak.
さらに、ブリッジで繋がれた２個のＮＯ型二座配位子が配位した白金原子を含む有機白金錯体が、結晶のような高密度状態で燐光を示すことも知られている（例えば、特許文献４）。また、非対称な２個のＮＯ型二座配位子が配位した白金原子を含む有機白金錯体も、結晶のような高密度状態で燐光を示すことも知られている（例えば、特許文献５）。
Furthermore, it is also known that an organic platinum complex containing a platinum atom coordinated by two NO-type bidentate ligands connected by a bridge exhibits phosphorescence in a high-density state like a crystal (for example, Patent Document 4). In addition, it is also known that an organic platinum complex containing a platinum atom coordinated with two asymmetrical NO-type bidentate ligands exhibits phosphorescence in a high-density state like a crystal (for example, Patent Document 5). ).
そこで、本発明は、固体であって、発光強度が強い発光材料を提供することを目的とする。
Therefore, an object of the present invention is to provide a light emitting material that is solid and has high emission intensity.
本発明は、式（Ｉ）で表される白金錯体を含む発光材料である。
The present invention is a light emitting material containing a platinum complex represented by the formula (I).
前記式中、Ａｒ１は、以下の式（ｉ）～（ｘｖｉｉ）のいずれかで表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、以下の式（ｘｘ）～（ｘｘｖｉ）のいずれかで表される式である。 In the above formula, Ar1 is a formula represented by any of the following formulas (i) to (xvii):
Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
環Ｘは、炭素原子ａとｂと一緒になって、以下の式（ｘｘ）～（ｘｘｖｉ）のいずれかで表される式である。 In the above formula, Ar1 is a formula represented by any of the following formulas (i) to (xvii):
Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
前記式中、Ｒ１およびＲ２は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、ハロゲン原子、炭素数１～１２のアルコキシ基、－ＮＨ2、－Ｎ（炭素数１～６のアルキル基）2、－ＯＨ、－ＣＯＯＨ、－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）、フェニル基、フェノキシ基、ニトリル基、ニトロ基、またはチオール基である。
なお、式（ｉ）～（ｘｉｉｉ）で表される式における置換基Ｒ１は、式（ｉ）～（ｘｉｉｉ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ１を有する場合、置換基Ｒ１はそれぞれ異なっていても、同一であってもよい。
式（ｘｘ）～（ｘｘｖ）で表される式における置換基Ｒ２は、式（ｘｘ）～（ｘｘｖ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ２を有する場合、置換基Ｒ２はそれぞれ異なっていても、同一であってもよい。 In the above formula, R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, or one carbon atom. ˜12 alkoxy group, —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C (═O) O— (alkyl group having 1 to 6 carbon atoms), phenyl Group, phenoxy group, nitrile group, nitro group, or thiol group.
The substituent R1 in the formulas represented by the formulas (i) to (xiii) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (i) to (xiii). In the case of having two or more substituents R1, the substituents R1 may be different or the same.
The substituent R2 in the formulas represented by the formulas (xx) to (xxv) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xx) to (xxv). When it has two or more substituents R2, the substituents R2 may be different or the same.
なお、式（ｉ）～（ｘｉｉｉ）で表される式における置換基Ｒ１は、式（ｉ）～（ｘｉｉｉ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ１を有する場合、置換基Ｒ１はそれぞれ異なっていても、同一であってもよい。
式（ｘｘ）～（ｘｘｖ）で表される式における置換基Ｒ２は、式（ｘｘ）～（ｘｘｖ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ２を有する場合、置換基Ｒ２はそれぞれ異なっていても、同一であってもよい。 In the above formula, R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, or one carbon atom. ˜12 alkoxy group, —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C (═O) O— (alkyl group having 1 to 6 carbon atoms), phenyl Group, phenoxy group, nitrile group, nitro group, or thiol group.
The substituent R1 in the formulas represented by the formulas (i) to (xiii) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (i) to (xiii). In the case of having two or more substituents R1, the substituents R1 may be different or the same.
The substituent R2 in the formulas represented by the formulas (xx) to (xxv) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xx) to (xxv). When it has two or more substituents R2, the substituents R2 may be different or the same.
また、本発明は、式（Ｘ）で表される白金錯体である。
Further, the present invention is a platinum complex represented by the formula (X).
前記式中、Ａｒ２は、以下の式（ｘｘｘｉ）～（ｘｘｘｘｖｉｉ）のいずれかで表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、以下の式（ｘｘ）～（ｘｘｖｉ）のいずれかで表される式である。 In the formula, Ar2 is a formula represented by any of the following formulas (xxxi) to (xxxvii):
Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
環Ｘは、炭素原子ａとｂと一緒になって、以下の式（ｘｘ）～（ｘｘｖｉ）のいずれかで表される式である。 In the formula, Ar2 is a formula represented by any of the following formulas (xxxi) to (xxxvii):
Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
前記式中、
Ｒ３は、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、ハロゲン原子、炭素数１～１２のアルコキシ基、－ＮＨ2、－Ｎ（炭素数１～６のアルキル基）2、－ＯＨ、－ＣＯＯＨ、－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）、フェニル基、フェノキシ基、ニトリル基、ニトロ基、またはチオール基であり、
Ｒ２およびＲ４は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、ハロゲン原子、炭素数１～１２のアルコキシ基、－ＮＨ2、－Ｎ（炭素数１～６のアルキル基）2、－ＯＨ、－ＣＯＯＨ、－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）、フェニル基、フェノキシ基、ニトリル基、ニトロ基、またはチオール基である。
なお、式（ｘｘｘｉ）で表される式における置換基Ｒ３は、式（ｘｘｘｉ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ３を有する場合、置換基Ｒ３はそれぞれ異なっていても、同一であってもよい。
式（ｘｘｘｉｉ）～（ｘｘｘｘｉｉｉ）で表される式における置換基Ｒ４は、式（ｘｘｘｉｉ）～（ｘｘｘｘｉｉｉ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ４を有する場合、置換基Ｒ４はそれぞれ異なっていても、同一であってもよい。
式（ｘｘ）～（ｘｘｖ）で表される式における置換基Ｒ２は、式（ｘｘ）～（ｘｘｖ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ２を有する場合、置換基Ｒ２はそれぞれ異なっていても、同一であってもよい。 In the above formula,
R3 is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, —NH 2 , —N (carbon An alkyl group having a number of 1 to 6) 2 , —OH, —COOH, —C (═O) O— (an alkyl group having 1 to 6 carbon atoms), a phenyl group, a phenoxy group, a nitrile group, a nitro group, or a thiol group And
R2 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, or an alkoxy having 1 to 12 carbon atoms. Group, —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C (═O) O— (alkyl group having 1 to 6 carbon atoms), phenyl group, phenoxy group , A nitrile group, a nitro group, or a thiol group.
Note that the substituent R3 in the formula represented by the formula (xxxi) may be replaced with one or more hydrogen atoms in the formula represented by the formula (xxxi). When it has two or more substituents R3, the substituents R3 may be different or the same.
The substituent R4 in the formulas represented by the formulas (xxxii) to (xxxiii) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xxxii) to (xxxiii). When it has two or more substituents R4, the substituents R4 may be different or the same.
The substituent R2 in the formulas represented by the formulas (xx) to (xxv) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xx) to (xxv). When it has two or more substituents R2, the substituents R2 may be different or the same.
Ｒ３は、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、ハロゲン原子、炭素数１～１２のアルコキシ基、－ＮＨ2、－Ｎ（炭素数１～６のアルキル基）2、－ＯＨ、－ＣＯＯＨ、－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）、フェニル基、フェノキシ基、ニトリル基、ニトロ基、またはチオール基であり、
Ｒ２およびＲ４は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、ハロゲン原子、炭素数１～１２のアルコキシ基、－ＮＨ2、－Ｎ（炭素数１～６のアルキル基）2、－ＯＨ、－ＣＯＯＨ、－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）、フェニル基、フェノキシ基、ニトリル基、ニトロ基、またはチオール基である。
なお、式（ｘｘｘｉ）で表される式における置換基Ｒ３は、式（ｘｘｘｉ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ３を有する場合、置換基Ｒ３はそれぞれ異なっていても、同一であってもよい。
式（ｘｘｘｉｉ）～（ｘｘｘｘｉｉｉ）で表される式における置換基Ｒ４は、式（ｘｘｘｉｉ）～（ｘｘｘｘｉｉｉ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ４を有する場合、置換基Ｒ４はそれぞれ異なっていても、同一であってもよい。
式（ｘｘ）～（ｘｘｖ）で表される式における置換基Ｒ２は、式（ｘｘ）～（ｘｘｖ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ２を有する場合、置換基Ｒ２はそれぞれ異なっていても、同一であってもよい。 In the above formula,
R3 is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, —NH 2 , —N (carbon An alkyl group having a number of 1 to 6) 2 , —OH, —COOH, —C (═O) O— (an alkyl group having 1 to 6 carbon atoms), a phenyl group, a phenoxy group, a nitrile group, a nitro group, or a thiol group And
R2 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, or an alkoxy having 1 to 12 carbon atoms. Group, —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C (═O) O— (alkyl group having 1 to 6 carbon atoms), phenyl group, phenoxy group , A nitrile group, a nitro group, or a thiol group.
Note that the substituent R3 in the formula represented by the formula (xxxi) may be replaced with one or more hydrogen atoms in the formula represented by the formula (xxxi). When it has two or more substituents R3, the substituents R3 may be different or the same.
The substituent R4 in the formulas represented by the formulas (xxxii) to (xxxiii) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xxxii) to (xxxiii). When it has two or more substituents R4, the substituents R4 may be different or the same.
The substituent R2 in the formulas represented by the formulas (xx) to (xxv) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xx) to (xxv). When it has two or more substituents R2, the substituents R2 may be different or the same.
本発明の白金錯体を含む発光材料は、固体であって、発光強度が強いという利点がある。
The light emitting material containing the platinum complex of the present invention is solid and has an advantage of high emission intensity.
本発明者らは、ビス（イミノフェノキシ）白金を母骨格とし、イミノ窒素原子に、嵩高い芳香環基を置換させると、結晶のような高密度の固体状態で強い発光強度を示すことを予想外に見出した。具体的には、下記式（Ｉ）において、Ａｒ１が芳香環基であれば、結晶中において分子が非πスタック型の構造をとり、その結果、発光強度が強くなることを見出した。一方、下記式（Ｉ）においてＡｒが鎖状アルキル基の場合、結晶中において発光強度は強くならないことも見出した。これらの知見に基づき、本発明者らは、本発明を完成した。なお、本発明において「固体」とは、結晶、ガラス等を意味する。また、本発明の白金錯体を含む発光材料は、固体であって、好ましくは室温において発光強度が強い。
The present inventors expect that, when bis (iminophenoxy) platinum is used as a mother skeleton and a bulky aromatic ring group is substituted for an imino nitrogen atom, strong emission intensity is exhibited in a high-density solid state such as a crystal. I found it outside. Specifically, in the following formula (I), it was found that if Ar1 is an aromatic ring group, the molecule has a non-π stack type structure in the crystal, and as a result, the emission intensity increases. On the other hand, it has also been found that in the following formula (I), when Ar is a chain alkyl group, the emission intensity does not increase in the crystal. Based on these findings, the present inventors have completed the present invention. In the present invention, “solid” means crystal, glass or the like. In addition, the light emitting material containing the platinum complex of the present invention is solid and preferably has high emission intensity at room temperature.
本発明の発光材料における白金錯体は、以下の式（Ｉ）で表される。
The platinum complex in the luminescent material of the present invention is represented by the following formula (I).
前記式中、Ａｒ１は、以下の式（ｉ）～（ｘｖｉｉ）のいずれかで表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、以下の式（ｘｘ）～（ｘｘｖｉ）のいずれかで表される式である。 In the above formula, Ar1 is a formula represented by any of the following formulas (i) to (xvii):
Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
環Ｘは、炭素原子ａとｂと一緒になって、以下の式（ｘｘ）～（ｘｘｖｉ）のいずれかで表される式である。 In the above formula, Ar1 is a formula represented by any of the following formulas (i) to (xvii):
Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
前記式中、Ｒ１およびＲ２は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、ハロゲン原子、炭素数１～１２のアルコキシ基、－ＮＨ2、－Ｎ（炭素数１～６のアルキル基）2、－ＯＨ、－ＣＯＯＨ、－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）、フェニル基、フェノキシ基、ニトリル基、ニトロ基、またはチオール基であり、好ましくは、水素原子、炭素数１～１２のアルキル基、ハロゲン原子または－Ｎ（炭素数１～６のアルキル基）2であり、より好ましくは、水素原子、炭素数１～１２のアルキル基またはハロゲン原子である。
In the above formula, R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, or one carbon atom. ˜12 alkoxy group, —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C (═O) O— (alkyl group having 1 to 6 carbon atoms), phenyl Group, phenoxy group, nitrile group, nitro group, or thiol group, preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or —N (an alkyl group having 1 to 6 carbon atoms) 2 And more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a halogen atom.
なお、式（ｉ）～（ｘｉｉｉ）で表される式における置換基Ｒ１は、式（ｉ）～（ｘｉｉｉ）で表される式中の１以上全ての水素原子と置き換えられてもよく、例えば、式（ｉ）～（ｘｉｉｉ）で表される式中の１～２の水素原子と置き換えられてもよい。２以上の置換基Ｒ１を有する場合、置換基Ｒ１はそれぞれ異なっていても、同一であってもよい。
The substituent R1 in the formulas represented by the formulas (i) to (xiii) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (i) to (xiii). , 1 to 2 hydrogen atoms in the formulas represented by formulas (i) to (xiii) may be substituted. In the case of having two or more substituents R1, the substituents R1 may be different or the same.
同様に、式（ｘｘ）～（ｘｘｖ）で表される式における置換基Ｒ２は、式（ｘｘ）～（ｘｘｖ）で表される式中の１以上全ての水素原子と置き換えられてもよく、例えば、式（ｘｘ）～（ｘｘｖ）で表される式中の１～２の水素原子と置き換えられてもよい。２以上の置換基Ｒ２を有する場合、置換基Ｒ２はそれぞれ異なっていても、同一であってもよい。
Similarly, the substituent R2 in the formulas represented by the formulas (xx) to (xxv) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xx) to (xxv), For example, one or two hydrogen atoms in the formulas represented by formulas (xx) to (xxv) may be substituted. When it has two or more substituents R2, the substituents R2 may be different or the same.
本発明において、用語「炭素数１～１２のアルキル基」とは、例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル等が挙げられる。アルキル基としては、直鎖状または分岐状であってもよい。炭素数１～１２のアルキル基としては、例えば、炭素数１～１０、好ましくは炭素数１～６、より好ましくは炭素数１～４のアルキル基である。
In the present invention, the term “alkyl group having 1 to 12 carbon atoms” includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like. The alkyl group may be linear or branched. The alkyl group having 1 to 12 carbon atoms is, for example, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.
本発明において、用語「炭素数２～１２のアルケニル基」とは、例えば、エチレニル、プロピレニル、ブテニル、ペンテニル、ヘキセニル等が挙げられる。アルケニル基としては、直鎖状または分岐状であってもよい。炭素数２～１２のアルケニル基としては、例えば、炭素数２～１０、好ましくは炭素数５～１０、より好ましくは炭素数５～８のアルケニル基である。
In the present invention, the term “C2-C12 alkenyl group” includes, for example, ethylenyl, propylenyl, butenyl, pentenyl, hexenyl and the like. The alkenyl group may be linear or branched. Examples of the alkenyl group having 2 to 12 carbon atoms include alkenyl groups having 2 to 10 carbon atoms, preferably 5 to 10 carbon atoms, and more preferably 5 to 8 carbon atoms.
本発明において、用語「炭素数２～１２のアルキニル基」とは、例えば、アセチレニル、プロペニル等が挙げられる。アルキニル基としては、直鎖状または分岐状であってもよい。炭素数２～１２のアルキニル基としては、例えば、炭素数２～１０、好ましくは炭素数５～１０、より好ましくは炭素数５～８のアルキニル基である。
In the present invention, the term “alkynyl group having 2 to 12 carbon atoms” includes, for example, acetylenyl, propenyl and the like. The alkynyl group may be linear or branched. The alkynyl group having 2 to 12 carbon atoms is, for example, an alkynyl group having 2 to 10 carbon atoms, preferably 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms.
本発明において、用語「炭素数１～１２のアルコキシ基」とは、アルキルオキシ基である。このアルキルオキシ基のアルキル部分は、前記炭素数１～１２のアルキル基と同様である。アルコキシル基としては、例えば、メトキシ、エトキシ、プロピルオキシ、ブチルオキシ、ペンチルオキシ、ヘキシルオキシ、ヘプチルオキシ、オクチルオキシ、ノニルオキシ、デシルオキシ、ウンデシルオキシ、ドデシルオキシ等が挙げられる。炭素数１～１２のアルコキシ基としては、例えば、炭素数１～１０、好ましくは炭素数５～１０、より好ましくは炭素数５～８のアルコキシ基である。
In the present invention, the term “alkoxy group having 1 to 12 carbon atoms” is an alkyloxy group. The alkyl part of the alkyloxy group is the same as the alkyl group having 1 to 12 carbon atoms. Examples of the alkoxyl group include methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy and the like. The alkoxy group having 1 to 12 carbon atoms is, for example, an alkoxy group having 1 to 10 carbon atoms, preferably 5 to 10 carbon atoms, and more preferably 5 to 8 carbon atoms.
本発明において、用語「－Ｎ（炭素数１～６のアルキル基）2」のアルキル基部分は、例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル等である。また、このアルキル部分は、互いに同一であっても、異なっていてもよい。－Ｎ（炭素数１～６のアルキル基）2としては、例えば、ジメチルアミノ、ジエチルアミノ、メチルエチルアミノイ、ジプロピルアミノ、ジブチルアミノ、ジペンチルアミノ、ジヘキシルアミノ等が挙げられる。アルキル基部分としては、直鎖状または分岐状であってもよい。－Ｎ（炭素数１～６のアルキル基）2としては、例えば、－Ｎ（炭素数１～５のアルキル基）2、好ましくは－Ｎ（炭素数１～４のアルキル基）2、より好ましくは－Ｎ（炭素数１～３のアルキル基）2である。
In the present invention, the alkyl group moiety of the term “—N (C 1-6 alkyl group) 2 ” is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl and the like. The alkyl moieties may be the same as or different from each other. Examples of —N (C 1-6 alkyl group) 2 include dimethylamino, diethylamino, methylethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino and the like. The alkyl group moiety may be linear or branched. —N (alkyl group having 1 to 6 carbon atoms) 2 is, for example, —N (alkyl group having 1 to 5 carbon atoms) 2 , preferably —N (alkyl group having 1 to 4 carbon atoms) 2 , more preferably Is —N (an alkyl group having 1 to 3 carbon atoms) 2 .
本発明において、用語「－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）」のアルキル基部分は、例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル等である。－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）としては、例えば、－Ｃ（＝Ｏ）Ｏ－メチル、－Ｃ（＝Ｏ）Ｏ－エチル、－Ｃ（＝Ｏ）Ｏ－プロピル、－Ｃ（＝Ｏ）Ｏ－ブチル、－Ｃ（＝Ｏ）Ｏ－ペンチル、－Ｃ（＝Ｏ）Ｏ－ヘキシル等が挙げられる。－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）としては、例えば、－Ｃ（＝Ｏ）Ｏ－（炭素数１～５のアルキル基）、好ましくは－Ｃ（＝Ｏ）Ｏ－（炭素数１～４のアルキル基）、より好ましくは－Ｃ（＝Ｏ）Ｏ－（炭素数１～３のアルキル基）である。
In the present invention, the alkyl group moiety of the term “—C (═O) O— (C 1-6 alkyl group)” is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl and the like. Examples of —C (═O) O— (an alkyl group having 1 to 6 carbon atoms) include —C (═O) O-methyl, —C (═O) O-ethyl, —C (═O) O. -Propyl, -C (= O) O-butyl, -C (= O) O-pentyl, -C (= O) O-hexyl and the like. Examples of —C (═O) O— (alkyl group having 1 to 6 carbon atoms) include —C (═O) O— (alkyl group having 1 to 5 carbon atoms), preferably —C (═O). O— (an alkyl group having 1 to 4 carbon atoms), more preferably —C (═O) O— (an alkyl group having 1 to 3 carbon atoms).
また、本発明の発光材料における白金錯体は、Ａｒ１は、式（ｉ）、式（ｉｉ）、式（ｉｉｉ）、式（ｉｖ）または式（ｖ）で表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）、式（ｘｘｉ）または式（ｘｘｉｉ）で表される式であり、
Ｒ１は、水素原子、ハロゲン原子、炭素数１～１２のアルキル基または－Ｎ（炭素数１～６のアルキル基）2であり、
式（ｉ）におけるＲ１は、式（ｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
式（ｉｉ）におけるＲ１は、式（ｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
式（ｉｉｉ）におけるＲ１は、式（ｉｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉｉｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
式（ｉｖ）におけるＲ１は、式（ｉｖ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉｖ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
式（ｖ）におけるＲ１は、式（ｖ）で表される式中の１または２の水素原子と置き換えられ、
式（ｖ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である式（Ｉ）の白金錯体がより好ましい。 In the platinum complex in the light emitting material of the present invention, Ar1 is a formula represented by the formula (i), the formula (ii), the formula (iii), the formula (iv), or the formula (v).
Ring X is a formula represented by the formula (xx), the formula (xxi) or the formula (xxii) together with the carbon atoms a and b.
R1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R1 in formula (i) is replaced with one or two hydrogen atoms in the formula represented by formula (i);
In the case of having two R1s in formula (i), the two R1s may be the same or different from each other,
R1 in formula (ii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (ii);
In the case of having two R1s in formula (ii), the two R1s may be the same or different from each other,
R1 in formula (iii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (iii);
In the case of having two R1s in formula (iii), the two R1s may be the same or different from each other,
R1 in formula (iv) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (iv);
In the case of having two R1s in formula (iv), the two R1s may be the same or different from each other,
R1 in formula (v) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (v);
In the case of having two R1s in formula (v), the two R1s may be the same or different from each other,
R2 is more preferably a platinum complex of the formula (I) which is a hydrogen atom.
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）、式（ｘｘｉ）または式（ｘｘｉｉ）で表される式であり、
Ｒ１は、水素原子、ハロゲン原子、炭素数１～１２のアルキル基または－Ｎ（炭素数１～６のアルキル基）2であり、
式（ｉ）におけるＲ１は、式（ｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
式（ｉｉ）におけるＲ１は、式（ｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
式（ｉｉｉ）におけるＲ１は、式（ｉｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉｉｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
式（ｉｖ）におけるＲ１は、式（ｉｖ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉｖ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
式（ｖ）におけるＲ１は、式（ｖ）で表される式中の１または２の水素原子と置き換えられ、
式（ｖ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である式（Ｉ）の白金錯体がより好ましい。 In the platinum complex in the light emitting material of the present invention, Ar1 is a formula represented by the formula (i), the formula (ii), the formula (iii), the formula (iv), or the formula (v).
Ring X is a formula represented by the formula (xx), the formula (xxi) or the formula (xxii) together with the carbon atoms a and b.
R1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R1 in formula (i) is replaced with one or two hydrogen atoms in the formula represented by formula (i);
In the case of having two R1s in formula (i), the two R1s may be the same or different from each other,
R1 in formula (ii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (ii);
In the case of having two R1s in formula (ii), the two R1s may be the same or different from each other,
R1 in formula (iii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (iii);
In the case of having two R1s in formula (iii), the two R1s may be the same or different from each other,
R1 in formula (iv) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (iv);
In the case of having two R1s in formula (iv), the two R1s may be the same or different from each other,
R1 in formula (v) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (v);
In the case of having two R1s in formula (v), the two R1s may be the same or different from each other,
R2 is more preferably a platinum complex of the formula (I) which is a hydrogen atom.
また、本発明の発光材料における白金錯体は、Ａｒ１は、式（ｉ）または（ｉｉ）で表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）で表される式であり、
Ｒ１は、水素原子、ハロゲン原子、炭素数１～１２のアルキル基または－Ｎ（炭素数１～６のアルキル基）2であり、
式（ｉ）におけるＲ１は、式（ｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
式（ｉｉ）におけるＲ１は、式（ｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である式（Ｉ）の白金錯体がより好ましい。
また、本発明の発光材料における白金錯体は、Ａｒ１は、式（ｉ）または（ｉｉ）で表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）で表される式であり、
Ｒ１は、水素原子、ハロゲン原子または炭素数１～１２のアルキル基であり、
式（ｉ）におけるＲ１は、式（ｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
式（ｉｉ）におけるＲ１は、式（ｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である式（Ｉ）の白金錯体がより好ましい。このような白金錯体は、室温において発光強度が強いためである。 Moreover, as for the platinum complex in the luminescent material of this invention, Ar1 is a formula represented by Formula (i) or (ii),
Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
R1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R1 in formula (i) is replaced with one or two hydrogen atoms in the formula represented by formula (i);
In the case of having two R1s in formula (i), the two R1s may be the same or different from each other,
R1 in formula (ii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (ii);
In the case of having two R1s in formula (ii), the two R1s may be the same or different from each other,
R2 is more preferably a platinum complex of the formula (I) which is a hydrogen atom.
Moreover, as for the platinum complex in the luminescent material of this invention, Ar1 is a formula represented by Formula (i) or (ii),
Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
R1 is a hydrogen atom, a halogen atom or an alkyl group having 1 to 12 carbon atoms,
R1 in formula (i) is replaced with one or two hydrogen atoms in the formula represented by formula (i);
In the case of having two R1s in formula (i), the two R1s may be the same or different from each other,
R1 in formula (ii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (ii);
In the case of having two R1s in formula (ii), the two R1s may be the same or different from each other,
R2 is more preferably a platinum complex of the formula (I) which is a hydrogen atom. This is because such a platinum complex has high emission intensity at room temperature.
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）で表される式であり、
Ｒ１は、水素原子、ハロゲン原子、炭素数１～１２のアルキル基または－Ｎ（炭素数１～６のアルキル基）2であり、
式（ｉ）におけるＲ１は、式（ｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
式（ｉｉ）におけるＲ１は、式（ｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である式（Ｉ）の白金錯体がより好ましい。
また、本発明の発光材料における白金錯体は、Ａｒ１は、式（ｉ）または（ｉｉ）で表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）で表される式であり、
Ｒ１は、水素原子、ハロゲン原子または炭素数１～１２のアルキル基であり、
式（ｉ）におけるＲ１は、式（ｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
式（ｉｉ）におけるＲ１は、式（ｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である式（Ｉ）の白金錯体がより好ましい。このような白金錯体は、室温において発光強度が強いためである。 Moreover, as for the platinum complex in the luminescent material of this invention, Ar1 is a formula represented by Formula (i) or (ii),
Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
R1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R1 in formula (i) is replaced with one or two hydrogen atoms in the formula represented by formula (i);
In the case of having two R1s in formula (i), the two R1s may be the same or different from each other,
R1 in formula (ii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (ii);
In the case of having two R1s in formula (ii), the two R1s may be the same or different from each other,
R2 is more preferably a platinum complex of the formula (I) which is a hydrogen atom.
Moreover, as for the platinum complex in the luminescent material of this invention, Ar1 is a formula represented by Formula (i) or (ii),
Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
R1 is a hydrogen atom, a halogen atom or an alkyl group having 1 to 12 carbon atoms,
R1 in formula (i) is replaced with one or two hydrogen atoms in the formula represented by formula (i);
In the case of having two R1s in formula (i), the two R1s may be the same or different from each other,
R1 in formula (ii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (ii);
In the case of having two R1s in formula (ii), the two R1s may be the same or different from each other,
R2 is more preferably a platinum complex of the formula (I) which is a hydrogen atom. This is because such a platinum complex has high emission intensity at room temperature.
また、本発明の発光材料における白金錯体は、例えば、以下の式で表される化合物が好ましい。これらの中で、温度変化によって発光強度が著しく低減しないことから、式（２）、（３）、（４）、（５）、（６）、（７）および（８）で表される化合物がより好ましく、式（３）および（６）の化合物がさらに好ましい。
In addition, the platinum complex in the light emitting material of the present invention is preferably a compound represented by the following formula, for example. Among these, the compounds represented by the formulas (2), (3), (4), (5), (6), (7) and (8) because the emission intensity is not significantly reduced by temperature change. Are more preferred, and compounds of formulas (3) and (6) are more preferred.
また、本発明の白金錯体は、以下の式（Ｘ）で表される。
The platinum complex of the present invention is represented by the following formula (X).
前記式中、Ａｒ２は、以下の式（ｘｘｘｉ）～（ｘｘｘｘｖｉｉ）のいずれかで表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、以下の式（ｘｘ）～（ｘｘｖｉ）のいずれかで表される式である。 In the formula, Ar2 is a formula represented by any of the following formulas (xxxi) to (xxxvii):
Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
環Ｘは、炭素原子ａとｂと一緒になって、以下の式（ｘｘ）～（ｘｘｖｉ）のいずれかで表される式である。 In the formula, Ar2 is a formula represented by any of the following formulas (xxxi) to (xxxvii):
Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
前記式中、
Ｒ３は、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、ハロゲン原子、炭素数１～１２のアルコキシ基、－ＮＨ2、－Ｎ（炭素数１～６のアルキル基）2、－ＯＨ、－ＣＯＯＨ、－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）、フェニル基、フェノキシ基、ニトリル基、ニトロ基、またはチオール基であり、好ましくは、炭素数１～１２のアルキル基、ハロゲン原子または－Ｎ（炭素数１～６のアルキル基）2であり、より好ましくは、炭素数１～１２のアルキル基またはハロゲン原子であり、
Ｒ２およびＲ４は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、ハロゲン原子、炭素数１～１２のアルコキシ基、－ＮＨ2、－Ｎ（炭素数１～６のアルキル基）2、－ＯＨ、－ＣＯＯＨ、－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）、フェニル基、フェノキシ基、ニトリル基、ニトロ基、またはチオール基であり、好ましくは、水素原子、炭素数１～１２のアルキル基、ハロゲン原子または－Ｎ（炭素数１～６のアルキル基）2であり、より好ましくは、水素原子、炭素数１～１２のアルキル基またはハロゲン原子である。 In the above formula,
R3 is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, —NH 2 , —N (carbon An alkyl group having a number of 1 to 6) 2 , —OH, —COOH, —C (═O) O— (an alkyl group having 1 to 6 carbon atoms), a phenyl group, a phenoxy group, a nitrile group, a nitro group, or a thiol group Preferably, it is an alkyl group having 1 to 12 carbon atoms, a halogen atom or —N (an alkyl group having 1 to 6 carbon atoms) 2 , more preferably an alkyl group having 1 to 12 carbon atoms or a halogen atom. Yes,
R2 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, or an alkoxy having 1 to 12 carbon atoms. Group, —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C (═O) O— (alkyl group having 1 to 6 carbon atoms), phenyl group, phenoxy group , A nitrile group, a nitro group, or a thiol group, preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom or —N (an alkyl group having 1 to 6 carbon atoms) 2 , more preferably , A hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a halogen atom.
Ｒ３は、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、ハロゲン原子、炭素数１～１２のアルコキシ基、－ＮＨ2、－Ｎ（炭素数１～６のアルキル基）2、－ＯＨ、－ＣＯＯＨ、－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）、フェニル基、フェノキシ基、ニトリル基、ニトロ基、またはチオール基であり、好ましくは、炭素数１～１２のアルキル基、ハロゲン原子または－Ｎ（炭素数１～６のアルキル基）2であり、より好ましくは、炭素数１～１２のアルキル基またはハロゲン原子であり、
Ｒ２およびＲ４は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、ハロゲン原子、炭素数１～１２のアルコキシ基、－ＮＨ2、－Ｎ（炭素数１～６のアルキル基）2、－ＯＨ、－ＣＯＯＨ、－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）、フェニル基、フェノキシ基、ニトリル基、ニトロ基、またはチオール基であり、好ましくは、水素原子、炭素数１～１２のアルキル基、ハロゲン原子または－Ｎ（炭素数１～６のアルキル基）2であり、より好ましくは、水素原子、炭素数１～１２のアルキル基またはハロゲン原子である。 In the above formula,
R3 is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, —NH 2 , —N (carbon An alkyl group having a number of 1 to 6) 2 , —OH, —COOH, —C (═O) O— (an alkyl group having 1 to 6 carbon atoms), a phenyl group, a phenoxy group, a nitrile group, a nitro group, or a thiol group Preferably, it is an alkyl group having 1 to 12 carbon atoms, a halogen atom or —N (an alkyl group having 1 to 6 carbon atoms) 2 , more preferably an alkyl group having 1 to 12 carbon atoms or a halogen atom. Yes,
R2 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, or an alkoxy having 1 to 12 carbon atoms. Group, —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C (═O) O— (alkyl group having 1 to 6 carbon atoms), phenyl group, phenoxy group , A nitrile group, a nitro group, or a thiol group, preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom or —N (an alkyl group having 1 to 6 carbon atoms) 2 , more preferably , A hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a halogen atom.
なお、式（ｘｘｘｉ）で表される式における置換基Ｒ３は、式（ｘｘｘｉ）で表される式中の１以上全ての水素原子と置き換えられてもよく、例えば、式（ｘｘｘｉ）で表される式中の１～２の水素原子と置き換えられてもよい。２以上の置換基Ｒ３を有する場合、置換基Ｒ３はそれぞれ異なっていても、同一であってもよい。
同様に、式（ｘｘｘｉｉ）～（ｘｘｘｘｉｉｉ）で表される式における置換基Ｒ４は、式（ｘｘｘｉｉ）～（ｘｘｘｘｉｉｉ）で表される式中の１以上全ての水素原子と置き換えられてもよく、例えば、式（ｘｘｘｉｉ）～（ｘｘｘｘｉｉｉ）で表される式中の１～２の水素原子と置き換えられてもよい。２以上の置換基Ｒ１を有する場合、置換基Ｒ１はそれぞれ異なっていても、同一であってもよい。 Note that the substituent R3 in the formula represented by the formula (xxxi) may be replaced with one or more hydrogen atoms in the formula represented by the formula (xxxi), for example, represented by the formula (xxxi). It may be replaced with 1 to 2 hydrogen atoms in the formula. When it has two or more substituents R3, the substituents R3 may be different or the same.
Similarly, the substituent R4 in the formulas represented by the formulas (xxxii) to (xxxiii) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xxxii) to (xxxiii), For example, it may be replaced with 1 to 2 hydrogen atoms in the formulas represented by the formulas (xxxii) to (xxxiii). In the case of having two or more substituents R1, the substituents R1 may be different or the same.
同様に、式（ｘｘｘｉｉ）～（ｘｘｘｘｉｉｉ）で表される式における置換基Ｒ４は、式（ｘｘｘｉｉ）～（ｘｘｘｘｉｉｉ）で表される式中の１以上全ての水素原子と置き換えられてもよく、例えば、式（ｘｘｘｉｉ）～（ｘｘｘｘｉｉｉ）で表される式中の１～２の水素原子と置き換えられてもよい。２以上の置換基Ｒ１を有する場合、置換基Ｒ１はそれぞれ異なっていても、同一であってもよい。 Note that the substituent R3 in the formula represented by the formula (xxxi) may be replaced with one or more hydrogen atoms in the formula represented by the formula (xxxi), for example, represented by the formula (xxxi). It may be replaced with 1 to 2 hydrogen atoms in the formula. When it has two or more substituents R3, the substituents R3 may be different or the same.
Similarly, the substituent R4 in the formulas represented by the formulas (xxxii) to (xxxiii) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xxxii) to (xxxiii), For example, it may be replaced with 1 to 2 hydrogen atoms in the formulas represented by the formulas (xxxii) to (xxxiii). In the case of having two or more substituents R1, the substituents R1 may be different or the same.
同様に、式（ｘｘ）～（ｘｘｖ）で表される式における置換基Ｒ２は、式（ｘｘ）～（ｘｘｖ）で表される式中の１以上全ての水素原子と置き換えられてもよく、例えば、式（ｘｘ）～（ｘｘｖ）で表される式中の１～２の水素原子と置き換えられてもよい。２以上の置換基Ｒ２を有する場合、置換基Ｒ２はそれぞれ異なっていても、同一であってもよい。
Similarly, the substituent R2 in the formulas represented by the formulas (xx) to (xxv) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xx) to (xxv), For example, one or two hydrogen atoms in the formulas represented by formulas (xx) to (xxv) may be substituted. When it has two or more substituents R2, the substituents R2 may be different or the same.
また、本発明の白金錯体は、Ａｒ１は、式（ｘｘｘｉ）、式（ｘｘｘｉｉ）、式（ｘｘｘｉｉｉ）、式（ｘｘｘｉｖ）または式（ｘｘｘｖ）で表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）、式（ｘｘｉ）または式（ｘｘｉｉ）で表される式であり、
Ｒ３は、ハロゲン原子、炭素数１～１２のアルキル基または－Ｎ（炭素数１～６のアルキル基）2であり、
式（ｘｘｘｉ）におけるＲ３は、式（ｘｘｘｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉ）において２つのＲ３を有する場合、２つのＲ３は、互いに同一であっても、異なっていてもよく、
Ｒ４は、水素原子、ハロゲン原子、炭素数１～１２のアルキル基または－Ｎ（炭素数１～６のアルキル基）2であり、
式（ｘｘｘｉｉ）におけるＲ４は、式（ｘｘｘｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉｉ）において２つのＲ４を有する場合、２つのＲ４は、互いに同一であっても、異なっていてもよく、
式（ｘｘｘｉｉｉ）におけるＲ４は、式（ｘｘｘｉｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉｉｉ）において２つのＲ４を有する場合、２つのＲ４は、互いに同一であっても、異なっていてもよく、
式（ｘｘｘｉｖ）におけるＲ４は、式（ｘｘｘｉｖ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉｖ）において２つのＲ４を有する場合、２つのＲ４は、互いに同一であっても、異なっていてもよく、
式（ｘｘｘｖ）におけるＲ４は、式（ｘｘｘｖ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｖ）において２つのＲ４を有する場合、２つのＲ４は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である式（Ｘ）の白金錯体がより好ましい。 In the platinum complex of the present invention, Ar1 is a formula represented by the formula (xxxi), the formula (xxxii), the formula (xxxiii), the formula (xxxiv), or the formula (xxxv).
Ring X is a formula represented by the formula (xx), the formula (xxi) or the formula (xxii) together with the carbon atoms a and b.
R3 is a halogen atom, an alkyl group having 1 to 12 carbon atoms, or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R3 in formula (xxxi) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxi);
In the case of having two R3 in the formula (xxxi), the two R3 may be the same or different from each other,
R4 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R4 in formula (xxxii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxii);
In the case of having two R4s in the formula (xxxii), the two R4s may be the same or different from each other,
R4 in formula (xxxiii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxiii);
In the case of having two R4s in the formula (xxxiii), the two R4s may be the same or different from each other,
R4 in formula (xxxiv) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxiv);
In the case of having two R4s in the formula (xxxiv), the two R4s may be the same or different from each other,
R4 in formula (xxxv) is replaced with one or two hydrogen atoms in the formula represented by formula (xxxv);
In the case of having two R4s in the formula (xxxv), the two R4s may be the same or different from each other,
R2 is more preferably a platinum complex of the formula (X) which is a hydrogen atom.
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）、式（ｘｘｉ）または式（ｘｘｉｉ）で表される式であり、
Ｒ３は、ハロゲン原子、炭素数１～１２のアルキル基または－Ｎ（炭素数１～６のアルキル基）2であり、
式（ｘｘｘｉ）におけるＲ３は、式（ｘｘｘｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉ）において２つのＲ３を有する場合、２つのＲ３は、互いに同一であっても、異なっていてもよく、
Ｒ４は、水素原子、ハロゲン原子、炭素数１～１２のアルキル基または－Ｎ（炭素数１～６のアルキル基）2であり、
式（ｘｘｘｉｉ）におけるＲ４は、式（ｘｘｘｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉｉ）において２つのＲ４を有する場合、２つのＲ４は、互いに同一であっても、異なっていてもよく、
式（ｘｘｘｉｉｉ）におけるＲ４は、式（ｘｘｘｉｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉｉｉ）において２つのＲ４を有する場合、２つのＲ４は、互いに同一であっても、異なっていてもよく、
式（ｘｘｘｉｖ）におけるＲ４は、式（ｘｘｘｉｖ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉｖ）において２つのＲ４を有する場合、２つのＲ４は、互いに同一であっても、異なっていてもよく、
式（ｘｘｘｖ）におけるＲ４は、式（ｘｘｘｖ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｖ）において２つのＲ４を有する場合、２つのＲ４は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である式（Ｘ）の白金錯体がより好ましい。 In the platinum complex of the present invention, Ar1 is a formula represented by the formula (xxxi), the formula (xxxii), the formula (xxxiii), the formula (xxxiv), or the formula (xxxv).
Ring X is a formula represented by the formula (xx), the formula (xxi) or the formula (xxii) together with the carbon atoms a and b.
R3 is a halogen atom, an alkyl group having 1 to 12 carbon atoms, or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R3 in formula (xxxi) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxi);
In the case of having two R3 in the formula (xxxi), the two R3 may be the same or different from each other,
R4 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R4 in formula (xxxii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxii);
In the case of having two R4s in the formula (xxxii), the two R4s may be the same or different from each other,
R4 in formula (xxxiii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxiii);
In the case of having two R4s in the formula (xxxiii), the two R4s may be the same or different from each other,
R4 in formula (xxxiv) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxiv);
In the case of having two R4s in the formula (xxxiv), the two R4s may be the same or different from each other,
R4 in formula (xxxv) is replaced with one or two hydrogen atoms in the formula represented by formula (xxxv);
In the case of having two R4s in the formula (xxxv), the two R4s may be the same or different from each other,
R2 is more preferably a platinum complex of the formula (X) which is a hydrogen atom.
本発明の白金錯体は、Ａｒ２は、式（ｘｘｘｉ）または（ｘｘｘｉｉ）で表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）で表される式であり、
Ｒ３は、炭素数１～１２のアルキル基、ハロゲン原子または－Ｎ（炭素数１～６のアルキル基）2であり、
Ｒ４は、水素原子、ハロゲン原子、炭素数１～１２のアルキル基または－Ｎ（炭素数１～６のアルキル基）2であり、
式（ｘｘｘｉ）におけるＲ３は、式（ｘｘｘｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉ）において２つのＲ３を有する場合、２つのＲ３は、互いに同一であっても、異なっていてもよく、
式（ｘｘｘｉｉ）におけるＲ４は、式（ｘｘｘｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉｉ）において２つのＲ４を有する場合、２つのＲ４は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である式（Ｘ）の白金錯体がより好ましい。
また、本発明の白金錯体は、Ａｒ２は、式（ｘｘｘｉ）または（ｘｘｘｉｉ）で表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）で表される式であり、
Ｒ３は、炭素数１～１２のアルキル基またはハロゲン原子であり、
Ｒ４は、水素原子、ハロゲン原子または炭素数１～１２のアルキル基であり、
式（ｘｘｘｉ）におけるＲ３は、式（ｘｘｘｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉ）において２つのＲ３を有する場合、２つのＲ３は、互いに同一であっても、異なっていてもよく、
式（ｘｘｘｉｉ）におけるＲ４は、式（ｘｘｘｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉｉ）において２つのＲ４を有する場合、２つのＲ４は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である式（Ｘ）の白金錯体がより好ましい。このような白金錯体は、室温において発光強度が強いためである。 In the platinum complex of the present invention, Ar2 is a formula represented by the formula (xxxi) or (xxxii),
Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
R3 is an alkyl group having 1 to 12 carbon atoms, a halogen atom or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R4 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R3 in formula (xxxi) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxi);
In the case of having two R3 in the formula (xxxi), the two R3 may be the same or different from each other,
R4 in formula (xxxii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxii);
In the case of having two R4s in the formula (xxxii), the two R4s may be the same or different from each other,
R2 is more preferably a platinum complex of the formula (X) which is a hydrogen atom.
In the platinum complex of the present invention, Ar2 is a formula represented by the formula (xxxi) or (xxxii),
Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
R3 is an alkyl group having 1 to 12 carbon atoms or a halogen atom,
R4 is a hydrogen atom, a halogen atom or an alkyl group having 1 to 12 carbon atoms,
R3 in formula (xxxi) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxi);
In the case of having two R3 in the formula (xxxi), the two R3 may be the same or different from each other,
R4 in formula (xxxii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxii);
In the case of having two R4s in the formula (xxxii), the two R4s may be the same or different from each other,
R2 is more preferably a platinum complex of the formula (X) which is a hydrogen atom. This is because such a platinum complex has high emission intensity at room temperature.
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）で表される式であり、
Ｒ３は、炭素数１～１２のアルキル基、ハロゲン原子または－Ｎ（炭素数１～６のアルキル基）2であり、
Ｒ４は、水素原子、ハロゲン原子、炭素数１～１２のアルキル基または－Ｎ（炭素数１～６のアルキル基）2であり、
式（ｘｘｘｉ）におけるＲ３は、式（ｘｘｘｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉ）において２つのＲ３を有する場合、２つのＲ３は、互いに同一であっても、異なっていてもよく、
式（ｘｘｘｉｉ）におけるＲ４は、式（ｘｘｘｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉｉ）において２つのＲ４を有する場合、２つのＲ４は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である式（Ｘ）の白金錯体がより好ましい。
また、本発明の白金錯体は、Ａｒ２は、式（ｘｘｘｉ）または（ｘｘｘｉｉ）で表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）で表される式であり、
Ｒ３は、炭素数１～１２のアルキル基またはハロゲン原子であり、
Ｒ４は、水素原子、ハロゲン原子または炭素数１～１２のアルキル基であり、
式（ｘｘｘｉ）におけるＲ３は、式（ｘｘｘｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉ）において２つのＲ３を有する場合、２つのＲ３は、互いに同一であっても、異なっていてもよく、
式（ｘｘｘｉｉ）におけるＲ４は、式（ｘｘｘｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉｉ）において２つのＲ４を有する場合、２つのＲ４は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である式（Ｘ）の白金錯体がより好ましい。このような白金錯体は、室温において発光強度が強いためである。 In the platinum complex of the present invention, Ar2 is a formula represented by the formula (xxxi) or (xxxii),
Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
R3 is an alkyl group having 1 to 12 carbon atoms, a halogen atom or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R4 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R3 in formula (xxxi) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxi);
In the case of having two R3 in the formula (xxxi), the two R3 may be the same or different from each other,
R4 in formula (xxxii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxii);
In the case of having two R4s in the formula (xxxii), the two R4s may be the same or different from each other,
R2 is more preferably a platinum complex of the formula (X) which is a hydrogen atom.
In the platinum complex of the present invention, Ar2 is a formula represented by the formula (xxxi) or (xxxii),
Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
R3 is an alkyl group having 1 to 12 carbon atoms or a halogen atom,
R4 is a hydrogen atom, a halogen atom or an alkyl group having 1 to 12 carbon atoms,
R3 in formula (xxxi) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxi);
In the case of having two R3 in the formula (xxxi), the two R3 may be the same or different from each other,
R4 in formula (xxxii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxii);
In the case of having two R4s in the formula (xxxii), the two R4s may be the same or different from each other,
R2 is more preferably a platinum complex of the formula (X) which is a hydrogen atom. This is because such a platinum complex has high emission intensity at room temperature.
また、本発明の白金錯体は、温度変化によって発光強度が著しく低減しないことから、式（２）、（３）、（４）、（５）、（６）、（７）および（８）で表される化合物がより好ましく、式（３）および（６）の化合物がさらに好ましい。
In addition, since the emission intensity of the platinum complex of the present invention is not significantly reduced by temperature change, the following formulas (2), (3), (4), (5), (6), (7) and (8) Compounds represented by formulas (3) and (6) are more preferred.
本発明の発光材料の白金錯体は、例えば、以下のようにして製造することができる。
The platinum complex of the light emitting material of the present invention can be produced, for example, as follows.
前記式中、Ａｒ１および環Ｘは、式（Ｉ）における定義と同様である。
In the above formula, Ar 1 and ring X are the same as defined in formula (I).
式（ＩＩ）の化合物と、白金化合物とを、塩基存在下に反応させて式（Ｉ）の化合物を得る。この白金化合物としては、例えば、ＰｔＣｌ2（ＣＨ3ＣＮ）2、Ｋ2ＰｔＣｌ4が挙げられる。塩基としては、例えばＫ2ＣＯ3、ＮａＨ、トリエチルアミン等を用いてもよい。この反応は、例えば２０～１３０℃で、１時間～４８時間、行う。この反応の溶媒としては、限定されないが、例えば、ジメチルホルムアミド（ＤＭＦ）とメタノールの混合物、ジメチルスルホキシド（ＤＭＳＯ）等が挙げられる。
A compound of formula (I) is reacted with a platinum compound in the presence of a base to give a compound of formula (I). Examples of the platinum compound include PtCl 2 (CH 3 CN) 2 and K 2 PtCl 4 . As the base, for example, K 2 CO 3 , NaH, triethylamine or the like may be used. This reaction is carried out, for example, at 20 to 130 ° C. for 1 to 48 hours. Examples of the solvent for this reaction include, but are not limited to, a mixture of dimethylformamide (DMF) and methanol, dimethyl sulfoxide (DMSO), and the like.
前記製造方法において、前記式（ＩＩ）で表される化合物は、市販で入手してもよいし、公知文献を参照して自家製造してもよい。式（ＩＩ）で表される化合物は、例えば、以下のようにして製造することができる。
In the production method, the compound represented by the formula (II) may be obtained commercially, or may be made in-house with reference to known literature. The compound represented by the formula (II) can be produced, for example, as follows.
前記式中、Ａｒ１および環Ｘは、式（Ｉ）における定義と同様である。
In the above formula, Ar 1 and ring X are the same as defined in formula (I).
式（ＩＩＩ）のサリチルアルデヒド誘導体と１当量のアミン（式（ＩＶ）の化合物）を、溶媒中で加熱することにより、式（ＩＩ）の化合物を得る。この反応は、例えば２０～１００℃で必要な時間、行う。この反応の溶媒としては、限定されないが、例えば、メタノール、ジメチルホルムアミド（ＤＭＦ）とメタノールの混合物、ジメチルスルホキシド（ＤＭＳＯ）等が挙げられる。
A compound of formula (II) is obtained by heating a salicylaldehyde derivative of formula (III) and 1 equivalent of an amine (compound of formula (IV)) in a solvent. This reaction is carried out, for example, at 20 to 100 ° C. for the necessary time. Examples of the solvent for this reaction include, but are not limited to, methanol, a mixture of dimethylformamide (DMF) and methanol, dimethyl sulfoxide (DMSO), and the like.
本発明の式（Ｘ）で表される白金錯体は、式（Ｉ）で表される白金錯体と同様にして製造することができる。
The platinum complex represented by the formula (X) of the present invention can be produced in the same manner as the platinum complex represented by the formula (I).
本発明の発光材料は、高輝度発光材料、および有機ＥＬ素子の発光材料、具体的には発光層の材料として用いることができる。そのような有機ＥＬ素子としては、例えば、基板、陽極、正孔輸送層、本発明の発光材料を含む発光層、電子輸送層、および陰極をこの順に積層して構成される。前記基板、陽極、正孔輸送層、電子輸送層、および陰極については、従来公知の材料を用い、従来公知の製造方法により形成されていてもよい。
The light-emitting material of the present invention can be used as a high-luminance light-emitting material and a light-emitting material of an organic EL element, specifically, a material of a light-emitting layer. As such an organic EL element, for example, a substrate, an anode, a hole transport layer, a light emitting layer containing the light emitting material of the present invention, an electron transport layer, and a cathode are laminated in this order. The substrate, the anode, the hole transport layer, the electron transport layer, and the cathode may be formed by a conventionally known manufacturing method using a conventionally known material.
前記発光層は、本発明の発光材料のほかに、ホスト材料を含んでいてもよい。このホスト材料としては、例えば、ジアリールアミン骨格を有するもの、ピリジン骨格を有するもの、ピラジン骨格を有するもの、トリアジン骨格を有するもの、アリールシラン骨格を有するものが挙げられる。
The light emitting layer may contain a host material in addition to the light emitting material of the present invention. Examples of the host material include those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an arylsilane skeleton.
以下に本発明を実施例によりさらに具体的に説明するが、本発明の範囲は、以下の実施例により限定されない。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the following examples.
種々のスペクトルは、以下の機器を用いて測定した。
核磁気共鳴（ＮＭＲ）スペクトルはバリアン社製ＵＮＩＴＹ－ＩＮＯＶＡ核磁気共鳴装置（５００ＭＨｚ）を用いて測定し、測定溶媒の残存シグナルを内部基準として使用した。 Various spectra were measured using the following instrument.
The nuclear magnetic resonance (NMR) spectrum was measured using a UNITY-INOVA nuclear magnetic resonance apparatus (500 MHz) manufactured by Varian, and the residual signal of the measurement solvent was used as an internal reference.
核磁気共鳴（ＮＭＲ）スペクトルはバリアン社製ＵＮＩＴＹ－ＩＮＯＶＡ核磁気共鳴装置（５００ＭＨｚ）を用いて測定し、測定溶媒の残存シグナルを内部基準として使用した。 Various spectra were measured using the following instrument.
The nuclear magnetic resonance (NMR) spectrum was measured using a UNITY-INOVA nuclear magnetic resonance apparatus (500 MHz) manufactured by Varian, and the residual signal of the measurement solvent was used as an internal reference.
量子収率は、蛍光光度計ＦＰ－６５００Ｎ、燐光測定対応低温中積分球システムＩＮＫ－５３３、および、液体試料用セルＬＰＨ－１２０（全て日本分光株式会社製）を用いて測定した。
The quantum yield was measured using a fluorometer FP-6500N, a low-temperature medium integrating sphere system INK-533 for phosphorescence measurement, and a liquid sample cell LPH-120 (all manufactured by JASCO Corporation).
本明細書の記載において、以下の略語を使用する。
ＤＭＳＯ：ジメチルスルホキシド The following abbreviations are used in the description of the present specification.
DMSO: Dimethyl sulfoxide
ＤＭＳＯ：ジメチルスルホキシド The following abbreviations are used in the description of the present specification.
DMSO: Dimethyl sulfoxide
［実施例１］
ｔｒａｎｓ－ビス（Ｎ－フェニルサリチルアルジミナト）白金（ＩＩ）（１）の合成 [Example 1]
Synthesis of trans-bis (N-phenylsalicylaldiminato) platinum (II) (1)
ｔｒａｎｓ－ビス（Ｎ－フェニルサリチルアルジミナト）白金（ＩＩ）（１）の合成 [Example 1]
Synthesis of trans-bis (N-phenylsalicylaldiminato) platinum (II) (1)
化合物（１）をスキーム１に従い、合成した。サリチルアルデヒド（ＩＩＩ－１）と１当量のアニリン（ＩＶ－１）をエタノール中で加熱還流することで合成したＮ－フェニルサリチルアルジミン配位子(ＩＩ-１)（６０５ｍｇ）と、ＰｔＣｌ2（ＣＨ3ＣＮ）2（５２９ｍｇ）、Ｋ2ＣＯ3（１．６８ｇ）をＤＭＳＯ（５ｍＬ）中、１１５℃で１６時間反応させた。前記混合物へジクロロメタン（５０ｍＬ）を加え、有機層を水（２０ｍＬ×３）で洗浄した。有機層を濃縮後、得られた残渣をシリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（１）を得た（オレンジ色粉末、２３０ｍｇ）。
Compound (1) was synthesized according to Scheme 1. N-phenylsalicylaldimine ligand (II-1) (605 mg) synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of aniline (IV-1) in ethanol, PtCl 2 (CH 3 CN) 2 (529mg), it was K 2 CO 3 a (1.68 g) in DMSO (5 mL), reacted for 16 hours at 115 ° C.. Dichloromethane (50 mL) was added to the mixture, and the organic layer was washed with water (20 mL × 3). After the organic layer was concentrated, the obtained residue was purified by silica gel column chromatography (eluent: CH 2 Cl 2 ) to obtain compound (1) (orange powder, 230 mg).
1H NMR (500 MHz, CDCl3) δ 6.12 (dm, J = 8.7 Hz, 2H), 6.52 (ddd, J = 8.0, 6.9, 1.1 Hz, 2H), 7.21 (ddd, J = 8.7, 6.9, 1.8 Hz, 2H), 7.23 (ddd, J = 8.0, 1.8 Hz, 2H), 7.35-7.39 (m, 6H), 7.41-7.45 (m, 4H), 8.01 (s, 2H);
HRMS (FAB+): m/z C26H20N2O2 195Ptについて計算値：587.1175, 測定値 587.1149。 1 H NMR (500 MHz, CDCl 3 ) δ 6.12 (dm, J = 8.7 Hz, 2H), 6.52 (ddd, J = 8.0, 6.9, 1.1 Hz, 2H), 7.21 (ddd, J = 8.7, 6.9, 1.8 Hz, 2H), 7.23 (ddd, J = 8.0, 1.8 Hz, 2H), 7.35-7.39 (m, 6H), 7.41-7.45 (m, 4H), 8.01 (s, 2H);
HRMS (FAB +): m / z Calculated for C 26 H 20 N 2 O 2 195 Pt: 587.1175, found 587.1149.
HRMS (FAB+): m/z C26H20N2O2 195Ptについて計算値：587.1175, 測定値 587.1149。 1 H NMR (500 MHz, CDCl 3 ) δ 6.12 (dm, J = 8.7 Hz, 2H), 6.52 (ddd, J = 8.0, 6.9, 1.1 Hz, 2H), 7.21 (ddd, J = 8.7, 6.9, 1.8 Hz, 2H), 7.23 (ddd, J = 8.0, 1.8 Hz, 2H), 7.35-7.39 (m, 6H), 7.41-7.45 (m, 4H), 8.01 (s, 2H);
HRMS (FAB +): m / z Calculated for C 26 H 20 N 2 O 2 195 Pt: 587.1175, found 587.1149.
［実施例２］
ｔｒａｎｓ－ビス（Ｎ－（２，６－ジメチルフェニル）サリチルアルジミナト）白金（ＩＩ）（２）の合成 [Example 2]
Synthesis of trans-bis (N- (2,6-dimethylphenyl) salicylaldiminato) platinum (II) (2)
ｔｒａｎｓ－ビス（Ｎ－（２，６－ジメチルフェニル）サリチルアルジミナト）白金（ＩＩ）（２）の合成 [Example 2]
Synthesis of trans-bis (N- (2,6-dimethylphenyl) salicylaldiminato) platinum (II) (2)
化合物（２）をスキーム２に従い、合成した。サリチルアルデヒド（ＩＩＩ－１）と１当量の２，６－ジメチルアニリン（ＩＶ－２）をエタノール中で加熱還流することで合成したＮ－（２，６－ジメチルフェニル）サリチルアルジミン配位子（ＩＩ－２）（４６１ｍｇ）と、ＰｔＣｌ2（ＣＨ3ＣＮ）2（３５７ｍｇ）、Ｋ2ＣＯ3（８５９ｍｇ）をＤＭＳＯ（５ｍＬ）中、１２０℃で１６時間反応させた。前記反応混合物へ酢酸エチル（１００ｍＬ）を加え、有機層を水（２０ｍＬ×３）で洗浄した。有機層を濃縮後、得られた残渣をＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（２）を得た（オレンジ色粉末、４６ｍｇ）。
Compound (2) was synthesized according to Scheme 2. N- (2,6-dimethylphenyl) salicylaldimine ligand (II) synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of 2,6-dimethylaniline (IV-2) in ethanol -2) (461 mg), PtCl 2 (CH 3 CN) 2 (357 mg), and K 2 CO 3 (859 mg) were reacted in DMSO (5 mL) at 120 ° C. for 16 hours. Ethyl acetate (100 mL) was added to the reaction mixture, and the organic layer was washed with water (20 mL × 3). The organic layer was concentrated and the resulting residue was purified by NH- silica gel column chromatography (eluent; CH 2 Cl 2) By, to thereby obtain compound (2) (orange powder, 46 mg).
1H NMR (500 MHz, CDCl3) δ 2.35 (s, 12H), 6.06 (d, J = 8.4 Hz, 2H), 6.48 (dd, J = 7.3, 7.3 Hz, 2H), 7.12-7.23 (m, 6H), 7.79 (s, 2H);
HRMS (FAB+): m/z C30H28N2O2 195Ptについて計算値：643.1802, 測定値 643.1827。 1 H NMR (500 MHz, CDCl 3 ) δ 2.35 (s, 12H), 6.06 (d, J = 8.4 Hz, 2H), 6.48 (dd, J = 7.3, 7.3 Hz, 2H), 7.12-7.23 (m, 6H), 7.79 (s, 2H);
HRMS (FAB +): m / z C 30 H 28 N 2 O 2 195 Pt for Calculated: 643.1802, measured 643.1827.
HRMS (FAB+): m/z C30H28N2O2 195Ptについて計算値：643.1802, 測定値 643.1827。 1 H NMR (500 MHz, CDCl 3 ) δ 2.35 (s, 12H), 6.06 (d, J = 8.4 Hz, 2H), 6.48 (dd, J = 7.3, 7.3 Hz, 2H), 7.12-7.23 (m, 6H), 7.79 (s, 2H);
HRMS (FAB +): m / z C 30 H 28 N 2 O 2 195 Pt for Calculated: 643.1802, measured 643.1827.
［実施例３］
ｔｒａｎｓ－ビス（Ｎ－（２，６－ジイソプロピルフェニル）サリチルアルジミナト）白金（ＩＩ）（３）の合成 [Example 3]
Synthesis of trans-bis (N- (2,6-diisopropylphenyl) salicylaldiminato) platinum (II) (3)
ｔｒａｎｓ－ビス（Ｎ－（２，６－ジイソプロピルフェニル）サリチルアルジミナト）白金（ＩＩ）（３）の合成 [Example 3]
Synthesis of trans-bis (N- (2,6-diisopropylphenyl) salicylaldiminato) platinum (II) (3)
化合物（３）をスキーム３に従い、合成した。サリチルアルデヒド（ＩＩＩ－１）と１当量の２，６－ジイソプロピルアニリン（ＩＶ－３）をエタノール中で加熱還流することで合成したＮ－（２，６－ジイソプロピルフェニル）サリチルアルジミン配位子（ＩＩ－２）（１．１２ｇ）と、ＰｔＣｌ2（ＣＨ3ＣＮ）2（６８４ｍｇ）、Ｋ2ＣＯ3（１．６６ｇ）をＤＭＳＯ（１０ｍＬ）中、１２０℃で１６時間反応させた。前記混合物へ酢酸エチル（１００ｍＬ）を加え、有機層を水（２０ｍＬ×３）で洗浄した。有機層を濃縮後、得られた残渣をＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（３）を得た（オレンジ色粉末、２３５ｍｇ）。
Compound (3) was synthesized according to Scheme 3. N- (2,6-diisopropylphenyl) salicylaldimine ligand (II) synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of 2,6-diisopropylaniline (IV-3) in ethanol -2) (1.12 g), PtCl 2 (CH 3 CN) 2 (684 mg) and K 2 CO 3 (1.66 g) were reacted in DMSO (10 mL) at 120 ° C. for 16 hours. Ethyl acetate (100 mL) was added to the mixture, and the organic layer was washed with water (20 mL × 3). After the organic layer was concentrated, the obtained residue was purified by NH-silica gel column chromatography (eluent: CH 2 Cl 2 ) to obtain compound (3) (orange powder, 235 mg).
1H NMR (500 MHz, CDCl3) δ 1.16 (d, J = 6.9 Hz, 12H), 1.25 (d, J = 6.9 Hz, 12H), 3.52 (spt, J = 6.9 Hz, 4H), 6.01 (d, J = 9.2 Hz, 2H), 6.46 (ddd, J = 7.8, 6.9, 1.1 Hz, 2H), 7.15-7.23 (m, 8H), 7.35 (dd, J = 7.5, 7.5 Hz, 2H), 7.83 (s, 2H);
HRMS (FAB+): m/z C38H44N2O2 195Ptについて計算値:755.3054, 測定値 755.3029。 1 H NMR (500 MHz, CDCl 3 ) δ 1.16 (d, J = 6.9 Hz, 12H), 1.25 (d, J = 6.9 Hz, 12H), 3.52 (spt, J = 6.9 Hz, 4H), 6.01 (d , J = 9.2 Hz, 2H), 6.46 (ddd, J = 7.8, 6.9, 1.1 Hz, 2H), 7.15-7.23 (m, 8H), 7.35 (dd, J = 7.5, 7.5 Hz, 2H), 7.83 ( s, 2H);
HRMS (FAB +): m / z Calculated for C 38 H 44 N 2 O 2 195 Pt: 755.3054, found 755.3029.
HRMS (FAB+): m/z C38H44N2O2 195Ptについて計算値:755.3054, 測定値 755.3029。 1 H NMR (500 MHz, CDCl 3 ) δ 1.16 (d, J = 6.9 Hz, 12H), 1.25 (d, J = 6.9 Hz, 12H), 3.52 (spt, J = 6.9 Hz, 4H), 6.01 (d , J = 9.2 Hz, 2H), 6.46 (ddd, J = 7.8, 6.9, 1.1 Hz, 2H), 7.15-7.23 (m, 8H), 7.35 (dd, J = 7.5, 7.5 Hz, 2H), 7.83 ( s, 2H);
HRMS (FAB +): m / z Calculated for C 38 H 44 N 2 O 2 195 Pt: 755.3054, found 755.3029.
［実施例４］
ｔｒａｎｓ－ビス（Ｎ－（１－ナフチル）サリチルアルジミナト）白金（ＩＩ）（４）の合成 [Example 4]
Synthesis of trans-bis (N- (1-naphthyl) salicylaldiminato) platinum (II) (4)
ｔｒａｎｓ－ビス（Ｎ－（１－ナフチル）サリチルアルジミナト）白金（ＩＩ）（４）の合成 [Example 4]
Synthesis of trans-bis (N- (1-naphthyl) salicylaldiminato) platinum (II) (4)
化合物（４）をスキーム４に従い、合成した。サリチルアルデヒド（ＩＩＩ－１）と１当量の１－ナフチルアミン（ＩＶ－４）をエタノール中で加熱還流することで合成したＮ－（１－ナフチル）サリチルアルジミン配位子（ＩＩ－４）（３５６ｍｇ）、ＰｔＣｌ2（ＣＨ3ＣＮ）2（２５２ｍｇ）、Ｋ2ＣＯ3（１．２９ｇ）、トルエン（９０ｍＬ）、ＤＭＳＯ（２３ｍＬ）の混合物を１２０℃で１６時間反応させた。前記混合物へ酢酸エチル（２００ｍＬ）を加え、有機層を水（５０ｍＬ×３）で洗浄した。有機層を濃縮後、得られた残渣をＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（４）を得た（オレンジ色粉末、２１２ｍｇ）。
Compound (4) was synthesized according to Scheme 4. N- (1-naphthyl) salicylaldimine ligand (II-4) (356 mg) synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of 1-naphthylamine (IV-4) in ethanol , PtCl 2 (CH 3 CN) 2 (252 mg), K 2 CO 3 (1.29 g), toluene (90 mL), DMSO (23 mL) were reacted at 120 ° C. for 16 hours. Ethyl acetate (200 mL) was added to the mixture, and the organic layer was washed with water (50 mL × 3). After concentration of the organic layer, the resulting residue was purified by NH-silica gel column chromatography (eluent: CH 2 Cl 2 ) to obtain compound (4) (orange powder, 212 mg).
1H NMR (500 MHz, CDCl3) δ 5.45 (d, J = 9.0 Hz, 2 H), 5.47 (d, J = 9.0 Hz, 2 H), 6.40 (ddd, J = 8.0, 6.9, 1.2 Hz, 2 H), 6.41 (ddd, J = 8.0, 6.9, 1.2 Hz, 2 H), 7.02 (ddd, J = 9.0, 6.9, 1.7 Hz, 2 H), 7.03 (ddd, J = 9.0, 6.9, 1.7 Hz, 2 H), 7.13 (dd, J = 8.0, 1.7 Hz, 2 H), 7.14 (dd, J = 8.0, 1.7 Hz, 2 H), 7.42 (dd, J = 7.2, 1.0 Hz, 2 H), 7.47 (dd, J = 7.2, 1.0 Hz, 2 H), 7.46-7.58 (m, 8 H), 7.46-7.58 (m, 8 H), 7.93 (dm, J = 7.2 Hz, 2 H), 7.94-7.97 (m, 2 H), 8.03 (s, 2 H), 8.04 (s, 2 H), 8.35 (dm, J = 7.2 Hz, 2 H), 8.41 (dm, J = 7.2 Hz, 2 H);
HRMS (FAB+): m/z C34H24N2O2 195Ptについて計算値:687.1489, 測定値 687.1458。 1 H NMR (500 MHz, CDCl 3 ) δ 5.45 (d, J = 9.0 Hz, 2 H), 5.47 (d, J = 9.0 Hz, 2 H), 6.40 (ddd, J = 8.0, 6.9, 1.2 Hz, 2 H), 6.41 (ddd, J = 8.0, 6.9, 1.2 Hz, 2 H), 7.02 (ddd, J = 9.0, 6.9, 1.7 Hz, 2 H), 7.03 (ddd, J = 9.0, 6.9, 1.7 Hz , 2 H), 7.13 (dd, J = 8.0, 1.7 Hz, 2 H), 7.14 (dd, J = 8.0, 1.7 Hz, 2 H), 7.42 (dd, J = 7.2, 1.0 Hz, 2 H), 7.47 (dd, J = 7.2, 1.0 Hz, 2 H), 7.46-7.58 (m, 8 H), 7.46-7.58 (m, 8 H), 7.93 (dm, J = 7.2 Hz, 2 H), 7.94- 7.97 (m, 2 H), 8.03 (s, 2 H), 8.04 (s, 2 H), 8.35 (dm, J = 7.2 Hz, 2 H), 8.41 (dm, J = 7.2 Hz, 2 H);
HRMS (FAB +): m / z C 34 H 24 N 2 O 2 195 Pt for Calculated: 687.1489, measured 687.1458.
HRMS (FAB+): m/z C34H24N2O2 195Ptについて計算値:687.1489, 測定値 687.1458。 1 H NMR (500 MHz, CDCl 3 ) δ 5.45 (d, J = 9.0 Hz, 2 H), 5.47 (d, J = 9.0 Hz, 2 H), 6.40 (ddd, J = 8.0, 6.9, 1.2 Hz, 2 H), 6.41 (ddd, J = 8.0, 6.9, 1.2 Hz, 2 H), 7.02 (ddd, J = 9.0, 6.9, 1.7 Hz, 2 H), 7.03 (ddd, J = 9.0, 6.9, 1.7 Hz , 2 H), 7.13 (dd, J = 8.0, 1.7 Hz, 2 H), 7.14 (dd, J = 8.0, 1.7 Hz, 2 H), 7.42 (dd, J = 7.2, 1.0 Hz, 2 H), 7.47 (dd, J = 7.2, 1.0 Hz, 2 H), 7.46-7.58 (m, 8 H), 7.46-7.58 (m, 8 H), 7.93 (dm, J = 7.2 Hz, 2 H), 7.94- 7.97 (m, 2 H), 8.03 (s, 2 H), 8.04 (s, 2 H), 8.35 (dm, J = 7.2 Hz, 2 H), 8.41 (dm, J = 7.2 Hz, 2 H);
HRMS (FAB +): m / z C 34 H 24 N 2 O 2 195 Pt for Calculated: 687.1489, measured 687.1458.
［実施例５］
ｔｒａｎｓ－ビス（Ｎ－（１－（２－メチル）ナフチル）サリチルアルジミナト）白金（ＩＩ）（５）の合成 [Example 5]
Synthesis of trans-bis (N- (1- (2-methyl) naphthyl) salicylaldiminato) platinum (II) (5)
ｔｒａｎｓ－ビス（Ｎ－（１－（２－メチル）ナフチル）サリチルアルジミナト）白金（ＩＩ）（５）の合成 [Example 5]
Synthesis of trans-bis (N- (1- (2-methyl) naphthyl) salicylaldiminato) platinum (II) (5)
化合物（５）をスキーム５に従い、合成した。サリチルアルデヒド（ＩＩＩ－１）と１当量の２－メチル－１－ナフチルアミン（ＩＶ－５）をエタノール中で加熱還流することで合成したＮ－（１－（２－メチル）ナフチル）サリチルアルジミン配位子（ＩＩ－５）（３６５ｍｇ）、ＰｔＣｌ2（ＣＨ3ＣＮ）2（２４３ｍｇ）、Ｋ2ＣＯ3（１．２６ｇ）、トルエン（９０ｍＬ）、ＤＭＳＯ（２３ｍＬ）の混合物を１２０℃で１６時間反応させた。前記混合物へ酢酸エチル（２００ｍＬ）を加え、有機層を水（５０ｍＬ×３）で洗浄した。有機層を濃縮後、得られた残渣をＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（５）を得た（オレンジ色粉末、２６７ｍｇ）。
Compound (5) was synthesized according to Scheme 5. N- (1- (2-methyl) naphthyl) salicylaldimine coordination synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of 2-methyl-1-naphthylamine (IV-5) in ethanol Reaction of a mixture of the child (II-5) (365 mg), PtCl 2 (CH 3 CN) 2 (243 mg), K 2 CO 3 (1.26 g), toluene (90 mL), DMSO (23 mL) at 120 ° C. for 16 hours I let you. Ethyl acetate (200 mL) was added to the mixture, and the organic layer was washed with water (50 mL × 3). After concentration of the organic layer, the resulting residue was purified by NH-silica gel column chromatography (eluent: CH 2 Cl 2 ) to obtain compound (5) (orange powder, 267 mg).
1H NMR (500 MHz, CDCl3) δ 2.55 (s, 6 H), 5.66 (d, J = 8.2 Hz, 2 H), 6.41 (dd, J = 8.0, 6.9 Hz, 2 H), 7.07 (dd, J = 9.0, 6.9 Hz, 2 H), 7.12 (d, J = 8.0 Hz, 2 H), 7.41-7.50 (m, 6 H), 7.83 (d, J = 8.2 Hz, 2 H), 7.88 (s, 2 H), 7.89 (d, J = 8.2 Hz, 2 H), 8.09 (dd, J = 8.2 Hz, 2 H);
HRMS (FAB): m/z C36H28N2O2 195Ptについて計算値: 715.1802, 測定値 715.1788。 1 H NMR (500 MHz, CDCl 3 ) δ 2.55 (s, 6 H), 5.66 (d, J = 8.2 Hz, 2 H), 6.41 (dd, J = 8.0, 6.9 Hz, 2 H), 7.07 (dd , J = 9.0, 6.9 Hz, 2 H), 7.12 (d, J = 8.0 Hz, 2 H), 7.41-7.50 (m, 6 H), 7.83 (d, J = 8.2 Hz, 2 H), 7.88 ( s, 2 H), 7.89 (d, J = 8.2 Hz, 2 H), 8.09 (dd, J = 8.2 Hz, 2 H);
HRMS (FAB): m / z C 36 H 28 N 2 O 2 195 Pt for Calculated: 715.1802, measured 715.1788.
HRMS (FAB): m/z C36H28N2O2 195Ptについて計算値: 715.1802, 測定値 715.1788。 1 H NMR (500 MHz, CDCl 3 ) δ 2.55 (s, 6 H), 5.66 (d, J = 8.2 Hz, 2 H), 6.41 (dd, J = 8.0, 6.9 Hz, 2 H), 7.07 (dd , J = 9.0, 6.9 Hz, 2 H), 7.12 (d, J = 8.0 Hz, 2 H), 7.41-7.50 (m, 6 H), 7.83 (d, J = 8.2 Hz, 2 H), 7.88 ( s, 2 H), 7.89 (d, J = 8.2 Hz, 2 H), 8.09 (dd, J = 8.2 Hz, 2 H);
HRMS (FAB): m / z C 36 H 28 N 2 O 2 195 Pt for Calculated: 715.1802, measured 715.1788.
［実施例６］
ｔｒａｎｓ－ビス（Ｎ－（１－（２－ブロモ）ナフチル）サリチルアルジミナト）白金（ＩＩ）（６）の合成 [Example 6]
Synthesis of trans-bis (N- (1- (2-bromo) naphthyl) salicylaldiminato) platinum (II) (6)
ｔｒａｎｓ－ビス（Ｎ－（１－（２－ブロモ）ナフチル）サリチルアルジミナト）白金（ＩＩ）（６）の合成 [Example 6]
Synthesis of trans-bis (N- (1- (2-bromo) naphthyl) salicylaldiminato) platinum (II) (6)
化合物（６）をスキーム６に従い、合成した。サリチルアルデヒド（ＩＩＩ－１）と１当量の２－ブロモ－１－ナフチルアミン（ＩＶ－６）をエタノール中で加熱還流することで合成したＮ－（１－（２－ブロモ）ナフチル）サリチルアルジミン配位子（ＩＩ－６）（３８６ｍｇ）、ＰｔＣｌ2（ＣＨ3ＣＮ）2（２０５ｍｇ）、Ｋ2ＣＯ3（１．０６ｇ）、トルエン（９０ｍＬ）、ＤＭＳＯ（２３ｍＬ）の混合物を１２０℃で１６時間反応させた。前記混合物へ酢酸エチル（２００ｍＬ）を加え、有機層を水（５０ｍＬ×３）で洗浄した。有機層を濃縮後、得られた残渣をＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（６）を得た（オレンジ色粉末、５０ｍｇ）。
Compound (6) was synthesized according to Scheme 6. N- (1- (2-bromo) naphthyl) salicylaldimine coordination synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of 2-bromo-1-naphthylamine (IV-6) in ethanol Reaction of a mixture of the child (II-6) (386 mg), PtCl 2 (CH 3 CN) 2 (205 mg), K 2 CO 3 (1.06 g), toluene (90 mL), DMSO (23 mL) at 120 ° C. for 16 hours I let you. Ethyl acetate (200 mL) was added to the mixture, and the organic layer was washed with water (50 mL × 3). After concentration of the organic layer, the resulting residue was purified by NH-silica gel column chromatography (eluent: CH 2 Cl 2 ) to obtain compound (6) (orange powder, 50 mg).
1H NMR (500 MHz, CDCl3) δ 5.60 (dm, J = 8.7 Hz, 2 H), 6.41 (ddd, J = 7.9, 6.9, 1.0 Hz, 2 H), 7.08 (ddd, J = 8.7, 6.9, 1.0 Hz, 2 H), 7.16 (dd, J = 7.9, 1.0 Hz, 2 H), 7.50-7.56 (m, 4 H), 7.76 (d, J = 8.8 Hz, 2 H), 7.79 (dd, J = 8.8, 8.8 Hz, 2 H), 7.89 (s, 2 H), 7.91 (ddm, J = 7.2, 2.2 Hz, 2 H), 8.28 (ddm, J = 7.2, 2.2 Hz, 2 H)。
1 H NMR (500 MHz, CDCl 3 ) δ 5.60 (dm, J = 8.7 Hz, 2 H), 6.41 (ddd, J = 7.9, 6.9, 1.0 Hz, 2 H), 7.08 (ddd, J = 8.7, 6.9 , 1.0 Hz, 2 H), 7.16 (dd, J = 7.9, 1.0 Hz, 2 H), 7.50-7.56 (m, 4 H), 7.76 (d, J = 8.8 Hz, 2 H), 7.79 (dd, J = 8.8, 8.8 Hz, 2 H), 7.89 (s, 2 H), 7.91 (ddm, J = 7.2, 2.2 Hz, 2 H), 8.28 (ddm, J = 7.2, 2.2 Hz, 2 H).
［実施例７］
ｔｒａｎｓ－ビス（Ｎ－（２，６－ジクロロフェニル）サリチルアルジミナト）白金（ＩＩ）（７）の合成 [Example 7]
Synthesis of trans-bis (N- (2,6-dichlorophenyl) salicylaldiminato) platinum (II) (7)
ｔｒａｎｓ－ビス（Ｎ－（２，６－ジクロロフェニル）サリチルアルジミナト）白金（ＩＩ）（７）の合成 [Example 7]
Synthesis of trans-bis (N- (2,6-dichlorophenyl) salicylaldiminato) platinum (II) (7)
化合物（７）をスキーム７に従い、合成した。サリチルアルデヒド（ＩＩＩ－１）と１当量の２，６－ジクロロアニリン（ＩＶ－８）をエタノール中で加熱還流することで合成したＮ－（２，６－ジクロロフェニル）サリチルアルジミン配位子(ＩＩ-８)（５３２ｍｇ）と、ＰｔＣｌ2（ＣＨ3ＣＮ）2（３４８ｍｇ）、Ｋ2ＣＯ3（８２９ｍｇ）をＤＭＳＯ（５ｍＬ）中、１１５℃で１６時間反応させた。前記混合物へジクロロメタン（５０ｍＬ）を加え、有機層を水（２０ｍＬ×３）で洗浄した。有機層を濃縮後、得られた残渣をシリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（７）を得た（オレンジ色粉末、５０ｍｇ）。
Compound (7) was synthesized according to Scheme 7. N- (2,6-dichlorophenyl) salicylaldimine ligand (II-) synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of 2,6-dichloroaniline (IV-8) in ethanol. 8) (532 mg), PtCl 2 (CH 3 CN) 2 (348 mg), and K 2 CO 3 (829 mg) were reacted in DMSO (5 mL) at 115 ° C. for 16 hours. Dichloromethane (50 mL) was added to the mixture, and the organic layer was washed with water (20 mL × 3). After the organic layer was concentrated, the obtained residue was purified by silica gel column chromatography (eluent: CH 2 Cl 2 ) to obtain compound (7) (orange powder, 50 mg).
1H NMR (500 MHz, CDCl3) δ6.05 (d, J = 8.7 Hz, 2H), 6.51 (dd, J = 7.1, 7.1 Hz, 2H), 7.22-7.31 (m, 4H), 7.45 (d, J = 8.2 Hz, 2H), 7.52-7.60 (m, 2H), 7.86 (s, 2H)。
1 H NMR (500 MHz, CDCl 3 ) δ6.05 (d, J = 8.7 Hz, 2H), 6.51 (dd, J = 7.1, 7.1 Hz, 2H), 7.22-7.31 (m, 4H), 7.45 (d , J = 8.2 Hz, 2H), 7.52-7.60 (m, 2H), 7.86 (s, 2H).
［実施例８］
ｔｒａｎｓ－ビス（Ｎ－（２，６－（Ｎ，Ｎ－ジメチルアミノ）フェニル）サリチルアルジミナト）白金（ＩＩ）（８）の合成 [Example 8]
Synthesis of trans-bis (N- (2,6- (N, N-dimethylamino) phenyl) salicylaldiminato) platinum (II) (8)
ｔｒａｎｓ－ビス（Ｎ－（２，６－（Ｎ，Ｎ－ジメチルアミノ）フェニル）サリチルアルジミナト）白金（ＩＩ）（８）の合成 [Example 8]
Synthesis of trans-bis (N- (2,6- (N, N-dimethylamino) phenyl) salicylaldiminato) platinum (II) (8)
化合物（８）をスキーム８に従い、合成した。サリチルアルデヒド（ＩＩＩ－１）と１当量の２，６－（Ｎ，Ｎ－ジメチルアミノ）アニリン（ＩＶ－９）をエタノール中で加熱還流することで合成したＮ－（２，６－（Ｎ，Ｎ－ジメチルアミノ））サリチルアルジミン配位子（ＩＩ－９）（５６６ｍｇ）と、ＰｔＣｌ2（ＣＨ3ＣＮ）2（３４８ｍｇ）、Ｋ2ＣＯ3（８２９ｍｇ）をＤＭＳＯ（５ｍＬ）中、１２０℃で１６時間反応させた。前記反応混合物へ酢酸エチル（１００ｍＬ）を加え、有機層を水（２０ｍＬ×３）で洗浄した。有機層を濃縮後、得られた残渣をＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（８）を得た（オレンジ色粉末、７ｍｇ）。
Compound (8) was synthesized according to Scheme 8. N- (2,6- (N, S) synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of 2,6- (N, N-dimethylamino) aniline (IV-9) in ethanol. N-dimethylamino)) salicylaldimine ligand (II-9) (566 mg), PtCl 2 (CH 3 CN) 2 (348 mg), K 2 CO 3 (829 mg) in DMSO (5 mL) at 120 ° C. The reaction was performed for 16 hours. Ethyl acetate (100 mL) was added to the reaction mixture, and the organic layer was washed with water (20 mL × 3). After concentration of the organic layer, the resulting residue was purified by NH-silica gel column chromatography (eluent: CH 2 Cl 2 ) to obtain compound (8) (orange powder, 7 mg).
1H NMR (500 MHz, CDCl3) δ2.77 (s, 12H), 6.02 (d, J = 8.5 Hz, 2H),6.40 (dd, J = 7.1, 7.1 Hz, 2H), 6.86 (d, J = 8.0 Hz, 4H), 7.10-7.24 (m, 6H), 7.85 (s, 2H); HRMS (FAB+): m/z C34H40N6O2
195Ptについて計算値：759.2860, 測定値 759.2859。
1 H NMR (500 MHz, CDCl 3 ) δ2.77 (s, 12H), 6.02 (d, J = 8.5 Hz, 2H), 6.40 (dd, J = 7.1, 7.1 Hz, 2H), 6.86 (d, J = 8.0 Hz, 4H), 7.10-7.24 (m, 6H), 7.85 (s, 2H); HRMS (FAB +): m / z Calculated for C 34 H 40 N 6 O 2 195 Pt: 759.2860, measured 759.2859 .
［比較例１］
ｔｒａｎｓ－ビス（Ｎ－ペンチルサリチルアルジミナト）白金（ＩＩ）（１１）の合成 [Comparative Example 1]
Synthesis of trans-bis (N-pentylsalicylaldiminato) platinum (II) (11)
ｔｒａｎｓ－ビス（Ｎ－ペンチルサリチルアルジミナト）白金（ＩＩ）（１１）の合成 [Comparative Example 1]
Synthesis of trans-bis (N-pentylsalicylaldiminato) platinum (II) (11)
化合物（１１）をスキーム９に従い、合成した。サリチルアルデヒド（ＩＩＩ－１）と１当量のペンチルアミン（ＩＶ－７）をエタノール中で加熱還流することで合成したＮ－ペンチルサリチルアルジミン配位子（ＩＩ－７）（１９１ｍｇ）と、ＰｔＣｌ2（ＣＨ3ＣＮ）2（１７４ｍｇ）、Ｋ2ＣＯ3（４６３ｍｇ）をＤＭＳＯ（３ｍＬ）中、１１０℃で２０時間反応させた。室温まで冷却したのち、水（９ｍＬ）を加え、生じた固体を吸引ろ過で集めた。ＮＨ－シリカゲルカラムクロマトグラフィ（溶出液；ＣＨ2Ｃｌ2）にて精製することで、化合物（１１）を得た（オレンジ色粉末、７７ｍｇ）。
Compound (11) was synthesized according to Scheme 9. N-pentylsalicylaldimine ligand (II-7) (191 mg) synthesized by heating and refluxing salicylaldehyde (III-1) and 1 equivalent of pentylamine (IV-7) in ethanol, PtCl 2 ( CH 3 CN) 2 (174 mg) and K 2 CO 3 (463 mg) were reacted in DMSO (3 mL) at 110 ° C. for 20 hours. After cooling to room temperature, water (9 mL) was added and the resulting solid was collected by suction filtration. Purification by NH-silica gel column chromatography (eluent; CH 2 Cl 2 ) gave Compound (11) (orange powder, 77 mg).
1H NMR (500 MHz, CDCl3) δ 0.87 (t, J = 6.9 Hz, 6 H), 1.20-1.45 (m, 20H), 1.82 (quin, J = 7.4 Hz, 4 H), 3.84 (t, J = 7.4 Hz, 4 H), 6.59 (t, J = 7.3 Hz, 2 H), 6.88 (d, J = 8.5 Hz, 2 H), 7.25 (dd, J = 7.5, 1.6 Hz, 2 H), 7.33 (td, J = 7.6, 1.8 Hz, 2 H), 7.91 (s, 2 H);
HRMS (FAB+) m/z [M+H]+ C30H45O2N2 194Ptについて計算値: 659.3108, 測定値: 659.3088。 1 H NMR (500 MHz, CDCl 3 ) δ 0.87 (t, J = 6.9 Hz, 6 H), 1.20-1.45 (m, 20H), 1.82 (quin, J = 7.4 Hz, 4 H), 3.84 (t, J = 7.4 Hz, 4 H), 6.59 (t, J = 7.3 Hz, 2 H), 6.88 (d, J = 8.5 Hz, 2 H), 7.25 (dd, J = 7.5, 1.6 Hz, 2 H), 7.33 (td, J = 7.6, 1.8 Hz, 2 H), 7.91 (s, 2 H);
HRMS (FAB + ) m / z [M + H] + Calculated for C 30 H 45 O 2 N 2 194 Pt: 659.3108, found: 659.3088.
HRMS (FAB+) m/z [M+H]+ C30H45O2N2 194Ptについて計算値: 659.3108, 測定値: 659.3088。 1 H NMR (500 MHz, CDCl 3 ) δ 0.87 (t, J = 6.9 Hz, 6 H), 1.20-1.45 (m, 20H), 1.82 (quin, J = 7.4 Hz, 4 H), 3.84 (t, J = 7.4 Hz, 4 H), 6.59 (t, J = 7.3 Hz, 2 H), 6.88 (d, J = 8.5 Hz, 2 H), 7.25 (dd, J = 7.5, 1.6 Hz, 2 H), 7.33 (td, J = 7.6, 1.8 Hz, 2 H), 7.91 (s, 2 H);
HRMS (FAB + ) m / z [M + H] + Calculated for C 30 H 45 O 2 N 2 194 Pt: 659.3108, found: 659.3088.
［固体発光量子収率の測定］
実施例１～８で得た化合物（１）～（８）および比較例１で得た化合物（１１）について、２９６Ｋおよび７７Ｋにおける固体発光量子収率φ（％）を測定した。具体的には、化合物（１）～（８）および化合物（１１）の結晶状態（粉末）における発光量子収率を、絶対法によりそれぞれ求めた。測定方法は以下の通りである。 [Measurement of solid-state luminescence quantum yield]
With respect to the compounds (1) to (8) obtained in Examples 1 to 8 and the compound (11) obtained in Comparative Example 1, the solid emission quantum yield φ (%) at 296K and 77K was measured. Specifically, the emission quantum yields of the compounds (1) to (8) and the compound (11) in the crystalline state (powder) were determined by the absolute method. The measuring method is as follows.
実施例１～８で得た化合物（１）～（８）および比較例１で得た化合物（１１）について、２９６Ｋおよび７７Ｋにおける固体発光量子収率φ（％）を測定した。具体的には、化合物（１）～（８）および化合物（１１）の結晶状態（粉末）における発光量子収率を、絶対法によりそれぞれ求めた。測定方法は以下の通りである。 [Measurement of solid-state luminescence quantum yield]
With respect to the compounds (1) to (8) obtained in Examples 1 to 8 and the compound (11) obtained in Comparative Example 1, the solid emission quantum yield φ (%) at 296K and 77K was measured. Specifically, the emission quantum yields of the compounds (1) to (8) and the compound (11) in the crystalline state (powder) were determined by the absolute method. The measuring method is as follows.
（測定方法）
測定の際、酸素の影響を除くため、全てのサンプルは、石英セル中に結晶（化合物（１）～（８）および化合物（１１））をそのまま封入して、アルゴン雰囲気下で測定した。さらに、低温（７７Ｋ）での測定は、石英製デュワーを用いて、結晶を封入した上記石英セルを液体窒素で冷やしながら測定した。全ての発光スペクトルは、標準光源を利用することにより補正を行った。励起光として４５０ｎｍの波長の光を用いた。内部量子収率の算出には、固体量子効率計算プログラム（日本分光株式会社製）を用いた。また、各白金錯体が発する光の発光極大波長も、併せて測定した。得られた測定結果を表１および表２に示す。なお、表１におけるデータは、約１ｍｇの結晶を測定して得られた結果であり、表２におけるデータは、約１０ｍｇの結晶を測定して得られた結果である。 (Measuring method)
At the time of measurement, in order to remove the influence of oxygen, all samples were measured in an argon atmosphere with crystals (compounds (1) to (8) and compound (11)) enclosed in a quartz cell as they were. Furthermore, the measurement at low temperature (77K) was performed using a quartz dewar while cooling the quartz cell in which the crystal was sealed with liquid nitrogen. All emission spectra were corrected by using a standard light source. Light having a wavelength of 450 nm was used as excitation light. For the calculation of the internal quantum yield, a solid quantum efficiency calculation program (manufactured by JASCO Corporation) was used. Moreover, the light emission maximum wavelength of the light emitted from each platinum complex was also measured. The obtained measurement results are shown in Tables 1 and 2. The data in Table 1 is a result obtained by measuring about 1 mg of crystals, and the data in Table 2 is a result obtained by measuring about 10 mg of crystals.
測定の際、酸素の影響を除くため、全てのサンプルは、石英セル中に結晶（化合物（１）～（８）および化合物（１１））をそのまま封入して、アルゴン雰囲気下で測定した。さらに、低温（７７Ｋ）での測定は、石英製デュワーを用いて、結晶を封入した上記石英セルを液体窒素で冷やしながら測定した。全ての発光スペクトルは、標準光源を利用することにより補正を行った。励起光として４５０ｎｍの波長の光を用いた。内部量子収率の算出には、固体量子効率計算プログラム（日本分光株式会社製）を用いた。また、各白金錯体が発する光の発光極大波長も、併せて測定した。得られた測定結果を表１および表２に示す。なお、表１におけるデータは、約１ｍｇの結晶を測定して得られた結果であり、表２におけるデータは、約１０ｍｇの結晶を測定して得られた結果である。 (Measuring method)
At the time of measurement, in order to remove the influence of oxygen, all samples were measured in an argon atmosphere with crystals (compounds (1) to (8) and compound (11)) enclosed in a quartz cell as they were. Furthermore, the measurement at low temperature (77K) was performed using a quartz dewar while cooling the quartz cell in which the crystal was sealed with liquid nitrogen. All emission spectra were corrected by using a standard light source. Light having a wavelength of 450 nm was used as excitation light. For the calculation of the internal quantum yield, a solid quantum efficiency calculation program (manufactured by JASCO Corporation) was used. Moreover, the light emission maximum wavelength of the light emitted from each platinum complex was also measured. The obtained measurement results are shown in Tables 1 and 2. The data in Table 1 is a result obtained by measuring about 1 mg of crystals, and the data in Table 2 is a result obtained by measuring about 10 mg of crystals.
前記表１に示すように、実施例１～６および比較例１の結果から、式（Ｉ）で表される白金錯体は、結晶状態において、室温において高い量子効率で燐光発光を示すことが確認できた。
As shown in Table 1, it was confirmed from the results of Examples 1 to 6 and Comparative Example 1 that the platinum complex represented by the formula (I) exhibits phosphorescence with high quantum efficiency at room temperature in the crystalline state. did it.
前記表２に示すように、実施例１～８および比較例１の結果から、式（Ｉ）で表される白金錯体は、結晶状態において、室温において高い量子効率で燐光発光を示すことが確認できた。
As shown in Table 2, the results of Examples 1 to 8 and Comparative Example 1 confirm that the platinum complex represented by the formula (I) exhibits phosphorescence with high quantum efficiency at room temperature in the crystalline state. did it.
［２－メチルテトラヒドロフラン溶液の７７Ｋガラスにおける発光量子収率発光の測定］
実施例１～８で得た化合物（１）～（８）について、２－メチルテトラヒドロフラン溶液の７７Ｋガラス状態における発光量子収率φ（％）を絶対法によりそれぞれ求めた。測定方法は以下の通りである。 [Measurement of Luminescence Quantum Yield Luminescence in 77K Glass of 2-Methyltetrahydrofuran Solution]
With respect to the compounds (1) to (8) obtained in Examples 1 to 8, the emission quantum yield φ (%) in the 77K glass state of the 2-methyltetrahydrofuran solution was determined by the absolute method. The measuring method is as follows.
実施例１～８で得た化合物（１）～（８）について、２－メチルテトラヒドロフラン溶液の７７Ｋガラス状態における発光量子収率φ（％）を絶対法によりそれぞれ求めた。測定方法は以下の通りである。 [Measurement of Luminescence Quantum Yield Luminescence in 77K Glass of 2-Methyltetrahydrofuran Solution]
With respect to the compounds (1) to (8) obtained in Examples 1 to 8, the emission quantum yield φ (%) in the 77K glass state of the 2-methyltetrahydrofuran solution was determined by the absolute method. The measuring method is as follows.
（測定方法）
石英セル中の、全てのサンプルの２－メチルテトラヒドロフラン溶液（２×１０-4Ｍ）は、酸素の影響を除くため脱気し、アルゴン雰囲気下とした。低温（７７Ｋ）での測定は、石英製デュワーを用いて、上記石英セルを液体窒素で冷やしながら測定した。全ての発光スペクトルは、標準光源を利用することにより補正を行った。励起光として４５０ｎｍの波長の光を用いた。内部量子収率の算出には、固体量子効率計算プログラム（日本分光株式会社製）を用いた。また、各白金錯体が発する光の発光極大波長も、併せて測定した。測定結果を表３に示す。 (Measuring method)
All 2-methyltetrahydrofuran solutions (2 × 10 −4 M) in the quartz cell were degassed to remove the influence of oxygen and placed in an argon atmosphere. The measurement at low temperature (77K) was performed using a quartz dewar while cooling the quartz cell with liquid nitrogen. All emission spectra were corrected by using a standard light source. Light having a wavelength of 450 nm was used as excitation light. For the calculation of the internal quantum yield, a solid quantum efficiency calculation program (manufactured by JASCO Corporation) was used. Moreover, the light emission maximum wavelength of the light emitted from each platinum complex was also measured. Table 3 shows the measurement results.
石英セル中の、全てのサンプルの２－メチルテトラヒドロフラン溶液（２×１０-4Ｍ）は、酸素の影響を除くため脱気し、アルゴン雰囲気下とした。低温（７７Ｋ）での測定は、石英製デュワーを用いて、上記石英セルを液体窒素で冷やしながら測定した。全ての発光スペクトルは、標準光源を利用することにより補正を行った。励起光として４５０ｎｍの波長の光を用いた。内部量子収率の算出には、固体量子効率計算プログラム（日本分光株式会社製）を用いた。また、各白金錯体が発する光の発光極大波長も、併せて測定した。測定結果を表３に示す。 (Measuring method)
All 2-methyltetrahydrofuran solutions (2 × 10 −4 M) in the quartz cell were degassed to remove the influence of oxygen and placed in an argon atmosphere. The measurement at low temperature (77K) was performed using a quartz dewar while cooling the quartz cell with liquid nitrogen. All emission spectra were corrected by using a standard light source. Light having a wavelength of 450 nm was used as excitation light. For the calculation of the internal quantum yield, a solid quantum efficiency calculation program (manufactured by JASCO Corporation) was used. Moreover, the light emission maximum wavelength of the light emitted from each platinum complex was also measured. Table 3 shows the measurement results.
前記表３に示すように、実施例１～８の結果から、式（Ｉ）で表される白金錯体は、ガラス状態において、高い量子収率で燐光発光を示すことが確認できた。
As shown in Table 3, from the results of Examples 1 to 8, it was confirmed that the platinum complex represented by the formula (I) exhibits phosphorescence with high quantum yield in the glass state.
［単結晶Ｘ線構造解析］
実施例１の化合物（１）、実施例３の化合物（３）、実施例４の化合物（４）および実施例６の化合物（６）について、株式会社リガク社製イメージングプレート単結晶自動Ｘ線構造解析装置ＰＡＰＩＤ－ＡＵＴＯを用いて単結晶Ｘ線結晶解析を行った。Ｘ線は、Ｍｏ－Ｋa線（λ＝０．７１０７５Å）を用いた。実施例１の化合物（１）、実施例３の化合物（３）および実施例６の化合物（６）は、ベンゼンにより、実施例４の化合物（４）は酢酸エチルにより結晶化した結晶を用いた。得られた実施例１の化合物（１）の結晶構造を図１に、実施例３の化合物（３）の結晶構造を図２に、実施例４の化合物（４）の結晶構造を図３に、実施例６の化合物（６）の結晶構造を図４に示す。また、結晶解析の結果得られた実施例３の化合物（３）の結晶中におけるパッキング図を図５に示す。 [Single-crystal X-ray structure analysis]
About the compound (1) of Example 1, the compound (3) of Example 3, the compound (4) of Example 4, and the compound (6) of Example 6, an imaging plate single crystal automatic X-ray structure manufactured by Rigaku Corporation Single crystal X-ray crystal analysis was performed using an analyzer PAAPID-AUTO. As the X-ray, a Mo—Ka ray (λ = 0.71075 mm) was used. The compound (1) of Example 1, the compound (3) of Example 3 and the compound (6) of Example 6 were crystallized with benzene, and the compound (4) of Example 4 was crystallized with ethyl acetate. . The crystal structure of the compound (1) obtained in Example 1 is shown in FIG. 1, the crystal structure of the compound (3) in Example 3 is shown in FIG. 2, and the crystal structure of the compound (4) in Example 4 is shown in FIG. The crystal structure of the compound (6) of Example 6 is shown in FIG. Moreover, the packing figure in the crystal | crystallization of the compound (3) of Example 3 obtained as a result of the crystal analysis is shown in FIG.
実施例１の化合物（１）、実施例３の化合物（３）、実施例４の化合物（４）および実施例６の化合物（６）について、株式会社リガク社製イメージングプレート単結晶自動Ｘ線構造解析装置ＰＡＰＩＤ－ＡＵＴＯを用いて単結晶Ｘ線結晶解析を行った。Ｘ線は、Ｍｏ－Ｋa線（λ＝０．７１０７５Å）を用いた。実施例１の化合物（１）、実施例３の化合物（３）および実施例６の化合物（６）は、ベンゼンにより、実施例４の化合物（４）は酢酸エチルにより結晶化した結晶を用いた。得られた実施例１の化合物（１）の結晶構造を図１に、実施例３の化合物（３）の結晶構造を図２に、実施例４の化合物（４）の結晶構造を図３に、実施例６の化合物（６）の結晶構造を図４に示す。また、結晶解析の結果得られた実施例３の化合物（３）の結晶中におけるパッキング図を図５に示す。 [Single-crystal X-ray structure analysis]
About the compound (1) of Example 1, the compound (3) of Example 3, the compound (4) of Example 4, and the compound (6) of Example 6, an imaging plate single crystal automatic X-ray structure manufactured by Rigaku Corporation Single crystal X-ray crystal analysis was performed using an analyzer PAAPID-AUTO. As the X-ray, a Mo—Ka ray (λ = 0.71075 mm) was used. The compound (1) of Example 1, the compound (3) of Example 3 and the compound (6) of Example 6 were crystallized with benzene, and the compound (4) of Example 4 was crystallized with ethyl acetate. . The crystal structure of the compound (1) obtained in Example 1 is shown in FIG. 1, the crystal structure of the compound (3) in Example 3 is shown in FIG. 2, and the crystal structure of the compound (4) in Example 4 is shown in FIG. The crystal structure of the compound (6) of Example 6 is shown in FIG. Moreover, the packing figure in the crystal | crystallization of the compound (3) of Example 3 obtained as a result of the crystal analysis is shown in FIG.
図１～４に示すように、実施例の白金錯体は、結晶中において、ビスイミノ白金錯体平面に対し、Ａｒ基が垂直方向に固定化された構造をとることが確認できた。また、図５に示すように、実施例の白金錯体は、結晶中において分子がπスタックしていない構造をとることが確認できた。
As shown in FIGS. 1 to 4, it was confirmed that the platinum complex of the example had a structure in which Ar groups were fixed in the vertical direction with respect to the plane of the biiminoplatinum complex in the crystal. Further, as shown in FIG. 5, it was confirmed that the platinum complex of the example had a structure in which the molecules were not stacked in the crystal.
このように、式（Ｉ）で表される化合物は、結晶中において、ビスイミノ白金錯体平面に対し、Ａｒ基が垂直方向に固定化された構造をとる。さらに、式（Ｉ）で表される化合物は、結晶中における分子の配列が非πスタック構造をとる。その結果、式（Ｉ）で表される化合物は結晶状態で分子間で消光しあわないため、強い強度の燐光発光が実現できると考えられる。
Thus, the compound represented by the formula (I) has a structure in which an Ar group is fixed in the vertical direction with respect to the plane of the bisiminoplatinum complex in the crystal. Furthermore, in the compound represented by the formula (I), the arrangement of molecules in the crystal has a non-π stack structure. As a result, since the compound represented by the formula (I) does not quench between molecules in a crystalline state, it is considered that strong intensity phosphorescence can be realized.
本発明の発光材料は、固体であって、かつ、発光効率に優れるため、実用に足る発光強度を得ることができる。従って、本発明の発光材料は、次世代技術である有機発光素子等の材料として有用である。
Since the light emitting material of the present invention is solid and has excellent light emission efficiency, it is possible to obtain light emission intensity sufficient for practical use. Therefore, the light-emitting material of the present invention is useful as a material for organic light-emitting elements that are the next generation technology.
Claims (6)
- 式（Ｉ）で表される白金錯体を含む発光材料。
環Ｘは、炭素原子ａとｂと一緒になって、以下の式（ｘｘ）～（ｘｘｖｉ）のいずれかで表される式である。
なお、式（ｉ）～（ｘｉｉｉ）で表される式における置換基Ｒ１は、式（ｉ）～（ｘｉｉｉ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ１を有する場合、置換基Ｒ１はそれぞれ異なっていても、同一であってもよい。
式（ｘｘ）～（ｘｘｖ）で表される式における置換基Ｒ２は、式（ｘｘ）～（ｘｘｖ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ２を有する場合、置換基Ｒ２はそれぞれ異なっていても、同一であってもよい。 A light emitting material containing a platinum complex represented by the formula (I).
Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
The substituent R1 in the formulas represented by the formulas (i) to (xiii) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (i) to (xiii). In the case of having two or more substituents R1, the substituents R1 may be different or the same.
The substituent R2 in the formulas represented by the formulas (xx) to (xxv) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xx) to (xxv). When it has two or more substituents R2, the substituents R2 may be different or the same. - Ａｒ１は、式（ｉ）または（ｉｉ）で表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）で表される式であり、
Ｒ１は、水素原子、ハロゲン原子、炭素数１～１２のアルキル基または－Ｎ（炭素数１～６のアルキル基）2であり、
式（ｉ）におけるＲ１は、式（ｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
式（ｉｉ）におけるＲ１は、式（ｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｉｉ）において２つのＲ１を有する場合、２つのＲ１は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である請求項１に記載の発光材料。 Ar1 is a formula represented by formula (i) or (ii),
Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
R1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R1 in formula (i) is replaced with one or two hydrogen atoms in the formula represented by formula (i);
In the case of having two R1s in formula (i), the two R1s may be the same or different from each other,
R1 in formula (ii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (ii);
In the case of having two R1s in formula (ii), the two R1s may be the same or different from each other,
The luminescent material according to claim 1, wherein R 2 is a hydrogen atom. - 式（Ｉ）で表される白金錯体が、式（１）～式（８）のいずれかで表される請求項１または２に記載の発光材料。
- 式（Ｘ）で表される白金錯体。
環Ｘは、炭素原子ａとｂと一緒になって、以下の式（ｘｘ）～（ｘｘｖｉ）のいずれかで表される式である。
Ｒ３は、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、ハロゲン原子、炭素数１～１２のアルコキシ基、－ＮＨ2、－Ｎ（炭素数１～６のアルキル基）2、－ＯＨ、－ＣＯＯＨ、－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）、フェニル基、フェノキシ基、ニトリル基、ニトロ基、またはチオール基であり、
Ｒ２およびＲ４は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、ハロゲン原子、炭素数１～１２のアルコキシ基、－ＮＨ2、－Ｎ（炭素数１～６のアルキル基）2、－ＯＨ、－ＣＯＯＨ、－Ｃ（＝Ｏ）Ｏ－（炭素数１～６のアルキル基）、フェニル基、フェノキシ基、ニトリル基、ニトロ基、またはチオール基である。
なお、式（ｘｘｘｉ）で表される式における置換基Ｒ３は、式（ｘｘｘｉ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ３を有する場合、置換基Ｒ３はそれぞれ異なっていても、同一であってもよい。
式（ｘｘｘｉｉ）～（ｘｘｘｘｉｉｉ）で表される式における置換基Ｒ４は、式（ｘｘｘｉｉ）～（ｘｘｘｘｉｉｉ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ４を有する場合、置換基Ｒ４はそれぞれ異なっていても、同一であってもよい。
式（ｘｘ）～（ｘｘｖ）で表される式における置換基Ｒ２は、式（ｘｘ）～（ｘｘｖ）で表される式中の１以上全ての水素原子と置き換えられてもよい。２以上の置換基Ｒ２を有する場合、置換基Ｒ２はそれぞれ異なっていても、同一であってもよい。 A platinum complex represented by the formula (X).
Ring X is a formula represented by any of the following formulas (xx) to (xxvi) together with carbon atoms a and b.
R3 is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, —NH 2 , —N (carbon An alkyl group having a number of 1 to 6) 2 , —OH, —COOH, —C (═O) O— (an alkyl group having 1 to 6 carbon atoms), phenyl group, phenoxy group, nitrile group, nitro group, or thiol group And
R2 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a halogen atom, or an alkoxy having 1 to 12 carbon atoms. Group, —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C (═O) O— (alkyl group having 1 to 6 carbon atoms), phenyl group, phenoxy group , A nitrile group, a nitro group, or a thiol group.
Note that the substituent R3 in the formula represented by the formula (xxxi) may be replaced with one or more hydrogen atoms in the formula represented by the formula (xxxi). When it has two or more substituents R3, the substituents R3 may be different or the same.
The substituent R4 in the formulas represented by the formulas (xxxii) to (xxxiii) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xxxii) to (xxxiii). When it has two or more substituents R4, the substituents R4 may be different or the same.
The substituent R2 in the formulas represented by the formulas (xx) to (xxv) may be replaced with one or more hydrogen atoms in the formulas represented by the formulas (xx) to (xxv). When it has two or more substituents R2, the substituents R2 may be different or the same. - Ａｒ２は、式（ｘｘｘｉ）または（ｘｘｘｉｉ）で表される式であり、
環Ｘは、炭素原子ａとｂと一緒になって、式（ｘｘ）で表される式であり、
Ｒ３は、炭素数１～１２のアルキル基、ハロゲン原子または－Ｎ（炭素数１～６のアルキル基）2であり、
Ｒ４は、水素原子、ハロゲン原子、炭素数１～１２のアルキル基または－Ｎ（炭素数１～６のアルキル基）2であり、
式（ｘｘｘｉ）におけるＲ３は、式（ｘｘｘｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉ）において２つのＲ３を有する場合、２つのＲ３は、互いに同一であっても、異なっていてもよく、
式（ｘｘｘｉｉ）におけるＲ４は、式（ｘｘｘｉｉ）で表される式中の１または２の水素原子と置き換えられ、
式（ｘｘｘｉｉ）において２つのＲ４を有する場合、２つのＲ４は、互いに同一であっても、異なっていてもよく、
Ｒ２は、水素原子である請求項４に記載の白金錯体。 Ar2 is a formula represented by the formula (xxxi) or (xxxii),
Ring X is a formula represented by formula (xx) together with carbon atoms a and b.
R3 is an alkyl group having 1 to 12 carbon atoms, a halogen atom or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R4 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or —N (an alkyl group having 1 to 6 carbon atoms) 2 ;
R3 in formula (xxxi) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxi);
In the case of having two R3 in the formula (xxxi), the two R3 may be the same or different from each other,
R4 in formula (xxxii) is replaced with 1 or 2 hydrogen atoms in the formula represented by formula (xxxii);
In the case of having two R4s in the formula (xxxii), the two R4s may be the same or different from each other,
The platinum complex according to claim 4, wherein R2 is a hydrogen atom. - 式（２）～式（８）のいずれかで表される請求項４または５に記載の白金錯体。
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| CN106478451A (en) * | 2016-09-18 | 2017-03-08 | 台州学院 | A kind of orange light luminescent material and preparation method thereof |
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| CN106478451A (en) * | 2016-09-18 | 2017-03-08 | 台州学院 | A kind of orange light luminescent material and preparation method thereof |
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