TW202043216A - Compound, light emitting material, and organic semiconductor laser element - Google Patents

Abstract

This compound represented by Z1-L-Z2 is highly stable and exhibits excellent light emitting properties. Z1 and Z2 each independently represent a substituted or unsubstituted diarylamino group. The two aryl groups forming the diarylamino group are bound to each other either directly or via a linking group. L represents a conjugated linking group including a benzofuran structure and includes five or more rings in the chain linking Z1 and Z2.

Description

Compounds, luminescent materials and organic semiconductor laser components

The present invention relates to a compound useful as a luminescent material.

At present, researches on organic semiconductor laser components with low laser oscillation threshold are prevalent. In particular, in order to realize such organic semiconductor laser elements, it is necessary to develop compounds that emit spontaneously emitted amplified light (ASE: Amplified Spontaneous Emissiom). Therefore, various compounds are actively synthesized, ASE characteristics are investigated, and compounds useful as laser materials are discovered Research. Among them, it can also be seen that by using the stilbene structure as the basic structure for molecular design, the study of laser materials with a lower threshold of spontaneous emission amplified light (ASE threshold) can be seen. For example, Non-Patent Document 1 reports that the bisstilbene derivative (BSB-Cz) represented by the following formula exhibits an extremely low ASE threshold and is excellent as an organic laser dye.

[先前技術文獻] [非專利文獻][化1]

[Prior technical literature] [Non-patent literature]

[Non-Patent Document 1] Appl. Phys. Lett. 2005, 86, 071110

[The problem to be solved by the invention]

As mentioned above, it is known that BSB-Cz is an excellent organic laser pigment. However, the inventors of the present invention evaluated the practicality of BSB-Cz. As a result, it was found that the double bond existing in the stilbene skeleton is chemically unstable. Therefore, if the light-emitting layer is formed by vapor deposition of BSB-Cz, it is During the evaporation process, cis-trans isomerization or decomposition occurs, and impurities such as isomers or decomposition products are generated (refer to the NMR (nuclear magnetic resonance) data of the examples described later). The generation of such impurities can lead to changes in optical properties or degradation of semiconductor characteristics. Therefore, in order to realize laser devices with excellent laser performance, it is highly desirable to develop laser materials with higher stability.

Under such circumstances, the inventors of the present invention have made repeated researches aiming at discovering compounds that exhibit the same or better luminescence characteristics as BSB-Cz or better than BSB-Cz and higher stability. In addition, intensive research is being conducted for the purpose of realizing organic semiconductor laser elements with a lower laser oscillation threshold. [Technical means to solve the problem]

As a result of intensive research, the inventors found that by linking the vinylidene group (-CH=CH-) of the stilbene structure of BSB-Cz to the benzene ring to form a furan ring, a stable Compounds with significantly improved performance, higher quantum yield and lower ASE threshold, and excellent stability. The present invention is proposed based on these findings, and specifically has the following configuration.

[上述群A之各基中之氫原子可經取代，＊表示連結位置，自上述群A之中選擇至少1個包含苯并呋喃結構之基，又，上述群A中之包含苯并呋喃結構之基及包含茀結構之基之構成該等基之苯環之環骨架構成原子之至少1個可經氮原子取代]。 [5]如[1]至[4]中任一項之化合物，其中上述共軛系連結基包含由下述通式(2)所表示之基， [化3]

[於通式(2)中，R¹ 及R² 相互鍵結而形成-O-，R³ 及R⁴ 分別獨立地表示氫原子或取代基，或相互鍵結而形成連結基，＊表示連結位置，通式(2)中之與苯環鍵結之氫原子可藉由取代基所取代]。 [6]如[1]至[5]中任一項之化合物，其中上述共軛系連結基之鏈長原子數為10～30。 [7]如[1]至[6]中任一項之化合物，其中Z¹ 及Z² 分別獨立地為由下述通式(3)所表示之基， [化4]

[於通式(3)中，R¹¹ ～R²⁰ 分別獨立地表示氫原子或取代基，R¹⁵ 及R¹⁶ 相互鍵結而形成單鍵或連結基，R¹¹ 及R¹² 、R¹² 及R¹³ 、R¹³ 及R¹⁴ 、R¹⁴ 及R¹⁵ 、R¹⁶ 及R¹⁷ 、R¹⁷ 及R¹⁸ 、R¹⁸ 及R¹⁹ 、R¹⁹ 及R²⁰ 可相互鍵結而形成環狀結構，＊表示鍵結位置]。 [8]如[1]至[6]中任一項之化合物，其中Z¹ 及Z² 分別獨立地為由下述通式(4)～(8)之任一者所表示之基， [化5]

[於通式(4)～(8)中，R²¹ ～R²⁴ 、R²⁷ ～R³⁸ 、R⁴¹ ～R⁴⁸ 、R⁵¹ ～R⁵⁸ 、R⁶¹ ～R⁶⁵ 、R⁸¹ ～R⁹⁰ 分別獨立地表示氫原子或取代基，R²¹ 及R²² 、R²² 及R²³ 、R²³ 及R²⁴ 、R²⁷ 及R²⁸ 、R²⁸ 及R²⁹ 、R²⁹ 及R³⁰ 、R³¹ 及R³² 、R³² 及R³³ 、R³³ 及R³⁴ 、R³⁵ 及R³⁶ 、R³⁶ 及R³⁷ 、R³⁷ 及R³⁸ 、R⁴¹ 及R⁴² 、R⁴² 及R⁴³ 、R⁴³ 及R⁴⁴ 、R⁴⁵ 及R⁴⁶ 、R⁴⁶ 及R⁴⁷ 、R⁴⁷ 及R⁴⁸ 、R⁵¹ 及R⁵² 、R⁵² 及R⁵³ 、R⁵³ 及R⁵⁴ 、R⁵⁵ 及R⁵⁶ 、R⁵⁶ 及R⁵⁷ 、R⁵⁷ 及R⁵⁸ 、R⁶¹ 及R⁶² 、R⁶² 及R⁶³ 、R⁶³ 及R⁶⁴ 、R⁶⁴ 及R⁶⁵ 、R⁵⁴ 及R⁶¹ 、R⁵⁵ 及R⁶⁵ 、R⁸¹ 及R⁸² 、R⁸² 及R⁸³ 、R⁸³ 及R⁸⁴ 、R⁸⁵ 及R⁸⁶ 、R⁸⁶ 及R⁸⁷ 、R⁸⁷ 及R⁸⁸ 、R⁸⁹ 及R⁹⁰ 可相互鍵結而形成環狀結構，＊表示鍵結位置]。 [9]如[8]之化合物，其中Z¹ 及Z² 分別獨立地為由上述通式(4)所表示之基。 [10]一種發光材料，其包含如[1]至[9]中任一項之化合物。 [11]如[10]之發光材料，其發射自發發射放大光。 [12]如[10]或[11]之發光材料，其係有機半導體雷射元件用之發光材料。 [13]一種有機半導體雷射元件，其包含由上述通式(1)所表示之化合物。 [發明之效果][1] A compound represented by the following general formula (1), the general formula (1) Z ¹ -LZ ² [In the general formula (1), Z ¹ and Z ² each independently represent substituted or unsubstituted A substituted diarylamino group, the two aryl groups constituting the above-mentioned diarylamino group are directly bonded to each other or via a linking group, L represents a conjugated linking group containing a benzofuran structure, and when Z ^{1 is} connected to The link chain of Z ² contains more than 5 rings]. [2] The compound of [1], wherein the above-mentioned conjugated linking group has a substituted or unsubstituted benzene ring, a substituted or unsubstituted furan ring, and a substituted or unsubstituted heteroaromatic ring , And a structure in which two or more of the substituted or unsubstituted vinylidene groups are connected (wherein the benzene ring and the furan ring may be condensed, and the furan ring and the heteroaromatic ring may be condensed). [3] The compound according to [1] or [2], wherein the above-mentioned conjugated linking group includes a substituted or unsubstituted benzofuran-2,6-diyl group. [4] The compound according to any one of [1] to [3], wherein the above-mentioned conjugated linking group has a structure in which one or more groups selected from the following group A are connected, [化2]

[The hydrogen atom in each group of the above group A may be substituted, * indicates the linking position, and at least one group containing a benzofuran structure is selected from the above group A, and the group A includes a benzofuran structure At least one of the atoms constituting the benzene ring of the benzene ring of the group and the group containing the fluorine structure may be substituted by a nitrogen atom]. [5] The compound according to any one of [1] to [4], wherein the above-mentioned conjugated system linking group includes a group represented by the following general formula (2), [化3]

[In the general formula (2), R ¹ and R ² are bonded to each other to form -O-, R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, or are bonded to each other to form a linking group, * represents a link Position, the hydrogen atom bonded to the benzene ring in the general formula (2) can be substituted by a substituent]. [6] The compound according to any one of [1] to [5], wherein the chain length of the conjugated linking group is 10-30. [7] The compound according to any one of [1] to [6], wherein Z ¹ and Z ² are each independently a group represented by the following general formula (3), [formation 4]

[In the general formula (3), R ¹¹ to R ²⁰ each independently represent a hydrogen atom or a substituent, R ¹⁵ and R ¹⁶ are bonded to each other to form a single bond or a linking group, R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ can be bonded to each other to form a cyclic structure, * represents a bond End position]. [8] The compound according to any one of [1] to [6], wherein Z ¹ and Z ² are each independently a group represented by any one of the following general formulas (4) to (8), [化5]

[In the general formulae (4) to (8), R ²¹ to R ²⁴ , R ²⁷ to R ³⁸ , R ⁴¹ to R ⁴⁸ , R ⁵¹ to R ⁵⁸ , R ⁶¹ to R ⁶⁵ , and R ⁸¹ to R ⁹⁰ are each independent Ground represents a hydrogen atom or a substituent, R ²¹ and R ²² , R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ and R ⁴⁴ , R ⁴⁵ And R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ , R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ , R ⁵⁷ and R ⁵⁸ , R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶³ and R ⁶⁴ , R ⁶⁴ and R ⁶⁵ , R ⁵⁴ and R ⁶¹ , R ⁵⁵ and R ⁶⁵ , R ⁸¹ and R ⁸² , R ⁸² and R ⁸³ , R ⁸³ and R ⁸⁴ , R ⁸⁵ and R ⁸⁶ , R ⁸⁶ and R ⁸⁷ , R ⁸⁷ and R ⁸⁸ , R ⁸⁹ and R ⁹⁰ can be bonded to each other to form a cyclic structure, and * indicates bonding position]. [9] The compound of [8], wherein Z ¹ and Z ² are each independently a group represented by the above general formula (4). [10] A luminescent material comprising the compound of any one of [1] to [9]. [11] Luminescent materials such as [10], which emit spontaneous emission amplified light. [12] The luminescent material of [10] or [11], which is a luminescent material for organic semiconductor laser devices. [13] An organic semiconductor laser element comprising the compound represented by the above general formula (1). [Effects of Invention]

Since the compound of the present invention exhibits a higher quantum yield and a lower ASE threshold, and higher stability, it is useful as a light-emitting material, especially as a light-emitting material for organic semiconductor laser devices. The use of the compound of the present invention in the organic semiconductor laser element of the laser material can achieve a lower laser oscillation threshold.

Hereinafter, the content of the present invention will be described in detail. The description of the constituent elements described below may be based on representative embodiments or specific examples of the present invention, however, the present invention is not limited to such embodiments or specific examples. In addition, in this specification, the numerical range indicated by "~" means a range that includes the numerical values described before and after "~" as the lower limit and the upper limit. In addition, the isotopic types of hydrogen atoms present in the molecule of the compound used in the present invention are not particularly limited. For example, all of the hydrogen atoms in the molecule may be ¹ H, or some or all of the hydrogen atoms may be ² H (deuterium D).

[Compound represented by general formula (1)] The compound of the present invention has a structure represented by the following general formula (1). General formula (1) Z ¹ -LZ ² In general formula (1), Z ¹ and Z ² each independently represent a substituted or unsubstituted diarylamino group, which constitutes two of the diarylamino groups The aryl groups are directly bonded to each other or bonded via a linking group. L represents a conjugated linking group including a benzofuran structure, and includes 5 or more rings in the linking chain linking Z ¹ and Z ² .

The L of the general formula (1) is a linking group in which the linking chain connecting Z ¹ and Z ² adopts a conjugated structure, includes at least one benzofuran structure, and includes 5 or more rings in the linking chain. The conjugated structure can be formed by connecting a structure having a double bond such as a benzene ring, a heteroaromatic ring, a furan ring, an vinylidene ring, and a benzofuran structure. The heteroaromatic ring referred to here is preferably a 5-membered ring or a 6-membered ring, and the heteroatom constituting the ring skeleton includes a nitrogen atom, an oxygen atom, and a sulfur atom. More preferably, a heteroaromatic ring system contains a nitrogen atom as a ring skeleton to form a 6-membered ring of heteroatoms and an oxygen atom as a ring skeleton to constitute a 5-membered ring of heteroatoms, for example, pyridine ring, pyrimidine ring, pyrimidine ring, and pyridine ring Ring, furan ring. Examples of the conjugated linking group that L can take include: those having a structure obtained by connecting two or more benzofuran structures; those having a structure obtained by connecting one or more benzofuran structures and one or more benzene rings. The structure; the structure obtained by connecting more than one benzofuran structure and more than one vinylidene structure; having more than one benzofuran structure, more than one benzene ring and more than one Structure derived from vinyl. The benzene ring and the furan ring constituting the conjugated linking group represented by L may be condensed, and the heteroaromatic ring and the furan ring may also be condensed. The conjugated linking group represented by L is preferably one having a structure in which one or more groups selected from the following group A are connected. [化6]

上述之中，特別是可選自以下之共軛連結基。

＊Indicates the link location. At least one group containing a benzofuran structure is selected from the above group A. In addition, at least one of the group A containing the benzofuran structure and the group containing the sulphur structure of the ring skeleton constituent atoms of the benzene ring constituting the group may be substituted with a nitrogen atom. The number of nitrogen atoms substituted in a ring is preferably 1 or 2. In the case of 2, it is preferably substituted at a position where the two nitrogen atoms are not directly bonded (non-adjacent positions). In this case, "including the benzofuran structure" means that it also includes another ring which condenses with the benzene ring constituting the benzofuran, or another ring which condenses with the furan ring constituting the benzofuran, or another ring separately Condensed with both the benzene ring and the furan ring constituting benzofuran. The condensed ring may be any of an aromatic ring, a heteroaromatic ring, a non-aromatic ring, and a heteronon-aromatic ring, and the number of rings is not particularly limited. The number of rings is, for example, selected from the range of 2-30, or selected from the range of 2-15, or selected from the range of 2-8. The conjugated linking group represented by L is preferably one containing the following benzofuran structure among the above-mentioned structures. [化7]

Among the above, in particular, the following conjugated linking groups can be selected.

Moreover, as the conjugated linking group represented by L, it is also preferable to include a structure represented by the following general formula (2). [化8]

In the general formula (2), R ¹ and R ² are bonded to each other to form -O-. R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, or are bonded to each other to form a linking group. ＊Indicates the link location. The hydrogen atom bonded to the benzene ring in the general formula (2) may be replaced by a substituent. The connecting group formed by R ³ and R ⁴ being bonded to each other is preferably -O-.

L includes more than 5 rings in the link chain connecting Z ¹ and Z ² . The "link chain" mentioned here does not include the branch structure. In addition, regarding the condensed ring, the number of condensed rings is counted. For example, if it is benzofuran, the ring count is 2, and if it is dibenzofuran, the ring count is 3. The number of rings included in the link chain connecting Z ¹ and Z ² can be, for example, 7 or more, or 9 or more, and 30 or less, or 20 or less, or 15 or less. The hydrogen atom in the benzene ring, heteroaromatic ring, furan ring, vinylidene, benzofuran structure, etc. constituting the conjugated linking group represented by L may be substituted by a substituent, and is preferably unsubstituted. As the substituent, for example, an alkyl group (the carbon number is preferably 1 to 20, more preferably 1 to 6), an alkenyl group (the carbon number is preferably 2 to 20, more preferably 2 to 6), and alkynyl groups (The carbon number is preferably 2-20, more preferably 2-6), aryl (the carbon number is preferably 6-20, more preferably 6-14), heteroaryl (the number of atoms constituting the ring skeleton is preferably 5-20, more preferably 5-14) etc. The substituents bonded to the benzene ring, heteroaromatic ring, furan ring, and benzofuran ring may be bonded to each other to form a cyclic structure. As such a cyclic structure, aromatic ring, heteroaromatic ring, non-aromatic hydrocarbon ring, non-aromatic heterocyclic ring, etc. are mentioned. On the other hand, the substituents of the vinylidene group may be bonded to each other to form a cyclic structure, but do not form an aromatic ring or a heteroaromatic ring, as long as it is a non-aromatic hydrocarbon ring or a non-aromatic heterocycle. The cyclic structure formed by bonding the substituents is preferably a 5- to 7-membered ring, and more preferably a 5- or 6-membered ring.

Z ¹ and Z ² in the general formula (1) each independently represent a substituted or unsubstituted diarylamino group, and the two aryl groups constituting the above-mentioned diarylamino group are bonded to each other directly or through a linking group . Z ¹ and Z ² may be the same or different, and are preferably the same. Furthermore, it is preferable that Z ¹ and Z ² are each independently a group represented by the following general formula (3). [化9]

In the general formula (3), R ¹¹ to R ²⁰ each independently represent a hydrogen atom or a substituent. R ¹⁵ and R ¹⁶ are bonded to each other to form a single bond or a linking group. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ can bond to each other Knot to form a ring structure. * Indicates the position of the bond. Regarding the substituents that R ¹¹ to R ²⁰ can take, refer to the description of the substituents such as the ring constituting the conjugated linking group represented by L. In addition, for the cyclic structure formed by bonding R ¹¹ and R ^{12 to} each other, refer to the description of the cyclic structure in the conjugated linking group represented by L.

As a preferable example of the group represented by the general formula (3), a group represented by any one of the following general formulas (4) to (8) can be cited. [化10]

In the general formulas (4) to (8), R ²¹ to R ²⁴ , R ²⁷ to R ³⁸ , R ⁴¹ to R ⁴⁸ , R ⁵¹ to R ⁵⁸ , R ⁶¹ to R ⁶⁵ , and R ⁸¹ to R ⁹⁰ are each independently Represents a hydrogen atom or a substituent. R ²¹ and R ²² , R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³¹ and R ³² , R ³² and R ³³ , R ³³ And R ³⁴ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ , R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ , R ⁵⁷ and R ⁵⁸ , R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶³ and R ⁶⁴ , R ⁶⁴ and R ⁶⁵ , R ⁵⁴ and R ⁶¹ , R ⁵⁵ and R ⁶⁵ , R ⁸¹ and R ⁸² , R ⁸² and R ⁸³ , R ⁸³ and R ⁸⁴ , R ⁸⁵ And R ⁸⁶ , R ⁸⁶ and R ⁸⁷ , R ⁸⁷ and R ⁸⁸ , R ⁸⁹ and R ⁹⁰ may be bonded to each other to form a cyclic structure. * Indicates the position of the bond. Regarding the substituents and cyclic structures mentioned here, reference can also be made to the description of the substituents and cyclic structures of L in the general formula (1). Among general formulas (4) to (8), those represented by general formula (4) are preferred.

As an example of the compound represented by general formula (1), for example, a compound represented by the following general formula (9) can be cited.

[化11]

In the general formula (9), R ¹ to R ⁸ each independently represent a hydrogen atom or a substituent, and at least 1 of R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ The groups are bonded to each other to form -O-. In the general formula (9), four groups of compounds are all forming -O-, and only R ¹ and R ² , R ⁷ and R ⁸ form -O-, or only R ³ and R ⁴ , R Compounds in which ⁵ and R ⁶ form -O- are also preferred. R ¹ to R ⁸ that do not form -O- in the general formula (9) are preferably hydrogen atoms. The hydrogen atom bonded to the benzene ring of the general formula (9) may be substituted by a substituent. In addition, two substituents may be bonded to each other to form a cyclic structure. Regarding the substituent, refer to the description of the substituent in L of the general formula (1). Regarding the cyclic structure, refer to the description of the cyclic structure in the conjugated linking group represented by L of the general formula (1).

Hereinafter, specific examples of the compound represented by the general formula (1) are illustrated. However, the compounds represented by the general formula (1) that can be used in the present invention should not be limitedly illustrated by these specific examples.

[化12]

[Synthesis method of compound represented by general formula (1)] The compound represented by general formula (1) is a novel compound. The compound represented by the general formula (1) can be synthesized by combining known reactions. For example, a compound in which R ¹ and R ² , R ⁷ and R ^{8 of the} general formula (9) are bonded to each other to form -O- can be synthesized by reacting two compounds shown in the following reaction formula (1). In addition, a compound in which R ³ and R ⁴ , R ⁵ and R ^{6 of the} general formula (1) are bonded to each other to form -O- can be synthesized by reacting two compounds shown in the following reaction formula (2).

[化13]

For the description of R ¹ to R ⁷ in the above reaction formula, refer to the corresponding description in the general formula (1). X ¹ to X ³ represent a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A chlorine atom, a bromine atom, and an iodine atom are preferable, and iodine is more preferable. The above reaction is to apply a known coupling reaction, and the known reaction conditions can be appropriately selected and used. For the details of the above reaction, the following synthesis example, Adv. Funct. Mater., 2018, 28, 4., Synthesis., 2008, 15, 2448., j. New. Chem., 2018, 42, 2446 ., J. Org. Chem., 2004, 69, 6832. For reference. In addition, the compound represented by the general formula (1) can also be synthesized by combining other known synthesis reactions.

之苯環之縮合結構(芳香族縮合環)之情形時，芳香性變大，發光性能本身發生變化。又，認為若將伸乙烯基藉由伸烷基而與苯環連結，則不增大芳香性，伸乙烯基併入環狀結構，穩定性提高。然而，於該情形時，產生合成步驟繁雜、或難以藉由蒸鍍成膜等問題。與此相對，本發明之由通式(1)所表示之化合物具有BSB-Cz所含之伸乙烯基之至少1個經由-O-與苯環連結而得之結構，藉此，成為伸乙烯基併入呋喃結構之形態。其中，認為呋喃環由於具有芳香性，故而穩定性高於伸乙烯基，另一方面，特別是由於呋喃環與苯環相比芳香性較低，故而即便呋喃環併入，亦保持茋之物性。又，藉由此種連結結構，雙鍵之順式反式異構化得以完全避免。 藉由以上，由通式(1)所表示之化合物除與BSB-Cz相同地表現出較低之ASE閾值以外，穩定性較高。進而，由通式(1)所表示之化合物有量子產率高於BSB-Cz之傾向。而且，有量子產率高於將BSB-Cz所含之伸乙烯基之至少1個經由-S-與苯環連結而形成噻吩環之化合物之傾向。又，由通式(1)所表示之化合物可不經歷繁雜之步驟而合成，又，可藉由真空蒸鍍法容易地成膜。藉由該等，由通式(1)所表示之化合物作為發光材料、特別是有機半導體雷射元件用之發光材料之有用性非常高。[Light-emitting material] The light-emitting material of the present invention is characterized by including a compound represented by the general formula (1). The compound represented by the general formula (1) is useful as a light-emitting material because it exhibits excellent light-emitting characteristics and high stability, and is particularly useful as a light-emitting material for organic laser devices due to its low ASE threshold. High sex. The reason is presumed to be that the compound represented by the general formula (1) has a structure common to BSB-Cz on one side, and is different from BSB-Cz on the other side, and has an vinylidene group (-CH=CH-) connected with a benzene ring to form furan The characteristic structure of the ring. That is, it can be seen that although BSB-Cz has a low ASE threshold, it is an excellent organic laser pigment, but has two highly reactive vinylidene groups (-CH=CH-) in the molecule, which is compared with aromatic compounds , Poor stability. However, in order to improve stability, Yu transformed the stilbene structure into

In the case of the condensed structure of the benzene ring (aromatic condensed ring), the aromaticity becomes greater and the luminescence performance itself changes. In addition, it is considered that if the vinylene group is connected to the benzene ring through the alkylene group, the aromaticity is not increased, the vinylene group is incorporated into the cyclic structure, and the stability is improved. However, in this case, problems such as complicated synthesis steps or difficulty in film formation by vapor deposition arise. In contrast, the compound represented by the general formula (1) of the present invention has a structure in which at least one of the vinylidene groups contained in BSB-Cz is connected to the benzene ring via -O-, thereby becoming vinylidene The form of the group incorporated into the furan structure. Among them, it is believed that the furan ring is more stable than vinylidene due to its aromaticity. On the other hand, especially because the furan ring is less aromatic than the benzene ring, even if the furan ring is incorporated, the physical properties of stilbene are maintained . Moreover, with this connection structure, the cis-trans isomerization of the double bond can be completely avoided. As a result of the above, the compound represented by the general formula (1) has higher stability except that it exhibits a lower ASE threshold like BSB-Cz. Furthermore, the compound represented by the general formula (1) tends to have a quantum yield higher than BSB-Cz. Moreover, there is a tendency that the quantum yield is higher than that of a compound that connects at least one of the vinylidene groups contained in BSB-Cz to a benzene ring via -S- to form a thiophene ring. In addition, the compound represented by the general formula (1) can be synthesized without going through complicated steps, and can be easily formed into a film by a vacuum vapor deposition method. With these, the compound represented by the general formula (1) is very useful as a light-emitting material, especially a light-emitting material for organic semiconductor laser devices.

[Organic Laser Components] As mentioned above, the compound represented by the general formula (1) exhibits a higher quantum yield, a lower ASE threshold, and a higher stability. Therefore, by using the compound represented by the general formula (1) in the material of the organic laser device, the optical properties can be achieved without damaging the optical properties during the deposition process during film formation, and excellent laser characteristics can be achieved. The organic laser element to which the compound of the present invention is applied can be a light-excited organic laser element that emits laser light by irradiating excitation light to the light-emitting layer, or it can be produced by injecting holes and electrons into the light-emitting layer and combining them A current-excited organic laser element (organic semiconductor laser element) that emits laser light with its energy. The light-excited organic laser device has a structure in which at least a light-emitting layer is formed on a substrate. In addition, the organic semiconductor laser element has a structure in which at least an anode, a cathode, and an organic layer located between the anode and the cathode are formed. The organic layer has at least a light-emitting layer, and may be composed of only the light-emitting layer, or may have one or more organic layers in addition to the light-emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer can be a hole injection transport layer with a hole injection function, and the electron transport layer can be an electron injection transport layer with an electron injection function. A specific example of the structure of the organic semiconductor laser device is shown in FIG. 1. In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is an electron transport layer, and 7 is a cathode. In the current-excited organic semiconductor laser element, the laser light generated in the light-emitting layer can be extracted to the outside through the anode, can be extracted to the outside through the cathode, and can also be extracted to the outside through the anode and the cathode. In addition, the laser light generated in the light-emitting layer can be extracted from the end surface of the organic layer to the outside. Hereinafter, each member and each layer of the organic semiconductor laser element will be described. Furthermore, the description of the substrate and the light-emitting layer is also applicable to the light-excited organic laser device and the light-emitting layer.

(Substrate) The organic semiconductor laser device of the present invention is preferably supported by a substrate. As the substrate, when the organic semiconductor laser element is configured to extract laser light from the substrate side, a substrate that is translucent to laser light is used, and a transparent substrate containing glass, transparent plastic, quartz, etc. is preferably used. On the other hand, when the organic semiconductor laser element is configured to extract laser light from the opposite side of the substrate, the substrate is not particularly limited. In addition to the above-mentioned transparent substrate, a substrate containing silicon, paper, and cloth can also be used.

(Anode) As the anode in the organic semiconductor laser element, it is suitable to use metals, alloys, conductive compounds and their mixtures with a large work function (above 4 eV) as electrode materials. Specific examples of such electrode materials include metals such as Au, CuI, indium tin oxide (ITO), SnO ₂ , ZnO, TiN, and other conductive transparent materials. In addition, it is also possible to use materials such as IDIXO (In ₂ O ₃ -ZnO) that are amorphous and can produce transparent conductive films. The anode can be formed by forming a film of these electrode materials by methods such as vapor deposition or sputtering. In addition, the anode can be formed by forming a pattern of the desired shape on the formed film by photolithography, or when the pattern accuracy is not required (about 100 μm or more), it can be used among the above-mentioned electrode materials. During evaporation or sputtering, a pattern is formed through a mask of the required shape. Alternatively, when using a coatable material such as an organic conductive compound, a wet film forming method such as a printing method and a coating method can also be used. Among them, when the organic semiconductor laser element is configured to extract laser light through the anode, the anode needs to be transparent to the laser light, and it is preferably constructed in a way that the transmittance of the laser light is greater than 1%, more preferably To be constituted with greater than 10%. Specifically, it is preferable to use the above-mentioned conductive transparent material for the anode, or to use a thin film obtained by forming a metal or alloy with a thickness of 10-100 nm for the anode. The sheet resistance as the anode is preferably several hundred Ω/□ or less. Furthermore, the film thickness also depends on the material, and is usually selected from the range of 10 to 1000 nm, preferably from 10 to 200 nm.

(Cathode) On the other hand, as a cathode, a metal (called an electron injecting metal), an alloy, a conductive compound, and a mixture of these whose work function is smaller than that of the material used in the anode can be used as the electrode material. As specific examples of such electrode materials, sodium, sodium-potassium alloys, magnesium, lithium, magnesium/copper mixtures, magnesium/silver mixtures, magnesium/aluminum mixtures, magnesium/indium mixtures, aluminum/alumina (Al ₂ O ₃ ) Mixtures, indium, lithium/aluminum mixtures, rare earth metals, etc. Among them, from the viewpoint of electron injectability and durability against oxidation, it is preferable that the electron injecting metal and the work function have a greater value than the stable metal that is a mixture of the second metal, such as magnesium/silver Mixtures, magnesium/aluminum mixtures, magnesium/indium mixtures, aluminum/alumina (Al ₂ O ₃ ) mixtures, lithium/aluminum mixtures, aluminum, etc. The cathode can be formed by forming a film of these electrode materials by methods such as vapor deposition or sputtering. Among them, when the organic semiconductor laser element is configured to extract the laser light through the cathode, the cathode needs to be transparent to the laser light, and it is preferably constructed in a way that the transmittance of the laser light is greater than 1%, and more preferably To be constituted with greater than 10%. Specifically, it is preferable to use a thin film obtained by forming the aforementioned electrode material with a thickness of 10-100 nm for the cathode. The sheet resistance of the cathode is preferably several hundred Ω/□ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

(Light-emitting layer) The light-emitting layer is a layer that generates excitons by recombining holes and electrons injected from each of the anode and the cathode, forming an inverted distribution, and emitting laser light. The light-emitting layer is preferably composed only of light-emitting materials, and may also include light-emitting materials and host materials. As the light-emitting material, one or two or more selected from the group of compounds represented by the general formula (1) can be used. In order to lower the threshold current density of the organic semiconductor laser device of the present invention, it is important to encapsulate at least one of the singlet excitons and triplet excitons generated by the luminescent material in the luminescent material. Therefore, it is preferable to use a host material in addition to the light-emitting material in the light-emitting layer. As the host material, at least any one of excited singlet energy and excited triplet energy can be used as an organic compound having a higher value than the compound represented by the general formula (1) used as a luminescent material. As a result, the singlet excitons and triplet excitons generated by the luminescent material can be enclosed in the molecules of the luminescent material, and the threshold current density for generating the emission of the laser light can be lowered. However, even if the singlet excitons and triplet excitons cannot be fully enclosed, it can contribute to the lowering of the threshold or the improvement of the laser characteristics. Therefore, if it is possible to achieve the lowering of the threshold or the improvement of the laser characteristics The host material can be used in the present invention without particular limitation. In the organic semiconductor laser element of the present invention, the laser light is emitted from the compound represented by the general formula (1) contained as a luminescent material. The laser light may be spontaneous emission amplified light, or stimulated emission light that is stimulated to be emitted by light irradiated from the outside. Also, the light from the light-emitting layer may include light emitted from the host material. When a host material not represented by the general formula (1) is used, the content of the compound represented by the general formula (1) used in the light-emitting material in the light-emitting layer is preferably 0.1% by weight or more, more preferably 1 % By weight or more, more preferably 50% by weight or less, more preferably 25% by weight or less, still more preferably 20% by weight or less, particularly preferably 15% by weight or less. As the host material in the light-emitting layer, it is preferably an organic compound that has hole transport ability, electron transport ability, prevents long-wavelength light emission, and has a higher glass transition temperature. Furthermore, the compound represented by the general formula (1) can also be used as the host material.

(Injection layer) The injection layer refers to a layer provided between the electrode and the organic layer in order to reduce the driving voltage or increase the luminescence brightness. There are a hole injection layer and an electron injection layer, which can exist between the anode and the light emitting layer or the hole transport layer, and Between the cathode and the light-emitting layer or electron transport layer. The injection layer can be set as needed.

(Barrier layer) The barrier layer is a layer that can prevent the charges (electrons or holes) and/or excitons existing in the light-emitting layer from diffusing out of the light-emitting layer. The electron blocking layer may be disposed between the light-emitting layer and the hole transport layer to block electrons from passing through the light-emitting layer to the hole transport layer. Similarly, the hole blocking layer can be disposed between the light-emitting layer and the electron transport layer to prevent holes from passing through the light-emitting layer to the electron transport layer. In addition, the barrier layer can be used to prevent excitons from diffusing to the outside of the light-emitting layer. That is, each of the electron blocking layer and the hole blocking layer may also function as an exciton blocking layer. The meaning of the electron blocking layer or exciton blocking layer in this specification refers to a layer having the functions of an electron blocking layer and an exciton blocking layer.

(Hole blocking layer) The hole blocking layer functions as an electron transport layer in a broad sense. The hole blocking layer has the function of transporting electrons and blocking holes from reaching the electron transport layer, thereby increasing the probability of recombination of electrons and holes in the light-emitting layer. As the material of the hole blocking layer, the material of the electron transport layer described later can be used as needed.

(Electron blocking layer) The electron blocking layer has the function of transmitting holes in a broad sense. The electron blocking layer has the function of transporting holes and blocking electrons from reaching the hole transport layer, thereby increasing the probability of recombination of electrons and holes in the light-emitting layer.

(Exciton blocking layer) The exciton blocking layer is a layer used to block the excitons generated by the recombination of holes and electrons in the light-emitting layer from diffusing to the charge transport layer. Through the insertion of this layer, the excitons can be efficiently sealed in the light-emitting layer. Can improve the luminous efficiency of the device. The exciton blocking layer may be inserted adjacent to the light-emitting layer on either the anode side or the cathode side, or may be inserted in both at the same time. That is, when there is an exciton blocking layer on the anode side, it can be inserted between the hole transport layer and the light-emitting layer adjacent to the light-emitting layer. When it is inserted on the cathode side, it can be inserted between the light-emitting layer and the cathode. The layer is inserted adjacent to the light-emitting layer. In addition, a hole injection layer or electron blocking layer can be provided between the anode and the exciton blocking layer adjacent to the anode side of the light-emitting layer, and the exciton blocking layer can be provided between the anode and the cathode side adjacent to the light-emitting layer In between, there are an electron injection layer, an electron transport layer, a hole blocking layer, etc. When the barrier layer is configured, it is preferable that at least one of the excited singlet energy and the excited triplet energy of the material used as the barrier layer is higher than the excited singlet energy and the excited triplet energy of the luminescent material.

(Hole transport layer) The hole transport layer includes a hole transport material with the function of transmitting holes, and the hole transport layer can be provided with a single layer or multiple layers. As the hole transport material, it has any of hole injection or transport, electron barrier properties, and can be either organic or inorganic. As well-known hole transport materials that can be used, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, Pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amine-substituted chalcone derivatives, azole derivatives, styrylanthracene derivatives, stellone derivatives , Hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, especially thiophene oligomers, etc. Preferably, porphyrin compounds and aromatic tertiary amine compounds are used And the styrylamine compound, it is more preferable to use an aromatic tertiary amine compound.

(Electron transport layer) The electron transport layer includes a material with the function of transporting electrons, and the electron transport layer can be provided with a single layer or multiple layers. As an electron transport material (also sometimes used as a hole blocking material), it can have the function of transferring electrons injected from the cathode to the light-emitting layer. As the electron transport layer that can be used, for example, nitro-substituted quinone derivatives, diphenyl quinone derivatives, thiopyran dioxide derivatives, carbodiimides, phenylenemethane derivatives, anthraquinone Dimethane and anthrone derivatives, oxadiazole derivatives, etc. Furthermore, among the above-mentioned oxadiazole derivatives, thiadiazole derivatives in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and quinoline derivatives having a quinoline ring known as an electron withdrawing group can also be used Used as an electronic transmission material. Furthermore, it is also possible to use a polymer material obtained by introducing these materials into a polymer chain or using these materials as the main chain of a polymer.

(Resonator structure) The organic semiconductor laser element of the present invention may further have a resonator structure. The "resonator structure" is a structure used to make the light emitted by the luminescent material reciprocate in the luminescent layer. In this way, the light moves repeatedly in the light-emitting layer to cause stimulated emission, and therefore, higher intensity laser light can be obtained. The resonator structure is specifically composed of a pair of mirrors. One mirror preferably has a reflectivity of 100%, and the other mirror preferably has a reflectivity of 50-95%. By setting the reflectivity of the other mirror to be relatively low, the laser light can be extracted to the outside through the mirror. Hereinafter, the mirror on the side that extracts the laser light is referred to as the "output mirror". The reflecting mirror and the output mirror can be arranged separately from the layers and parts of the above-mentioned organic semiconductor laser element, and the anode or the cathode can also function as a reflecting mirror or an output mirror.

For example, when the anode has the function of a mirror or an output mirror, the anode is preferably composed of a metal film that absorbs less visible light, has a higher reflectivity, and has a relatively large work function (above 4.0 eV). As such a metal film, for example, a metal film such as Ag, Pt, and Au, or an alloy film containing these metals can be cited. The reflectance and transmittance of the anode can be adjusted to desired values by, for example, controlling the thickness of the metal film within a range of tens of nm or more. When the cathode has the function of a mirror or an output mirror, the cathode is preferably composed of a metal film that absorbs less visible light, has a higher reflectivity, and has a smaller work function. As such a metal film, for example, metal films such as Al and Mg, or alloy films containing these metals can be cited. The reflectance and transmittance of the cathode can be adjusted to desired values by, for example, controlling the thickness of the metal film within a range of tens of nm or more. When the reflector or output mirror is separated from the above-mentioned layers and parts, it is preferable to form a reflective film between the anode and the organic layer or between the substrate and the anode to function as a reflector or output mirror . When a reflecting mirror or an output mirror is provided between the anode and the organic layer, as these materials, it is better to use visible light that absorbs less, obtains higher reflectivity, and has a larger work function (work function 4.0 eV and above) conductive materials. Specifically, a metal film including metals such as Ag, Pt, Au, or an alloy containing these metals can be used as a reflecting mirror or an output mirror. The reflectance and transmittance of the reflecting mirror or the output mirror can be adjusted to desired values by, for example, controlling the thickness of the metal film within a range of tens of nm or more. Among them, when the reflector or output mirror is arranged between the anode and the organic layer, the material of the anode does not need to be a material with a larger work function, and known electrode materials can be widely used. When a reflecting mirror or an output mirror is provided between the substrate and the anode, as these materials, it is preferable to use those that absorb less visible light and can obtain higher reflectivity. Specifically, a metal film including metals such as Al, Ag, Pt, or an alloy containing these metals, a laminated film obtained by laminating a Ti film on an alloy film of Al and Si, and alternating silicon oxide and titanium oxide can be used The dielectric multilayer film formed by the film is used as a reflecting mirror or an output mirror. Among them, the reflectance and transmittance of the metal film can be adjusted to desired values by, for example, controlling the film thickness within a range of tens of nm or more. In addition, the reflectance and transmittance of the dielectric multilayer film are adjusted to desired values by controlling the film thickness and the number of layers of silicon oxide and titanium oxide. As a combination of a reflector and an output mirror, one can include: the output mirror is an anode and the reflector is a cathode; the output mirror is a reflective film arranged between the anode and the organic layer or between the substrate and the anode, and the reflector is The combination of the cathode; the reflection mirror is the combination of the anode and the output mirror the cathode; the reflection mirror is the reflective film arranged between the anode and the organic layer or between the substrate and the anode, and the output mirror is the combination of the cathode. In this type of resonator structure, it is preferable to use the total optical film thickness of the layers between the reflector and the output mirror (the total of the values obtained by multiplying the respective film thickness of each layer by the refractive index) as the laser light To design the layer structure of the component in the way of integer multiples of the half wavelength. Thereby, a standing wave is formed between the reflecting mirror and the output mirror, the light is amplified, and a higher intensity laser light can be obtained.

In addition, the above resonator structure is one that reciprocates the laser light in a direction perpendicular to the main surface of the substrate, and the resonator structure can also be one that reciprocates the laser light in a direction horizontal to the main surface of the substrate. This kind of resonator structure can use the reflection obtained by the refractive index difference between the organic layer and the air, and the end surface of the organic layer can be configured as a reflecting mirror or an output mirror. In addition, it is also possible to set a diffraction grating at a grating interval of λ/2n (λ: wavelength of light, n: an integer greater than 1) near the light-emitting layer, so that the light generated in the light-emitting layer passes through the grating of the diffraction grating Periodic reflections at intervals. In the present invention, both the aspect of emitting light from the end surface of the organic layer and the aspect of emitting light in the direction perpendicular to the organic layer (substrate) can be adopted. For example, it can be exemplified that a two-dimensional DFB (distributed feedback) diffraction grating structure is formed on a substrate to emit light in a direction perpendicular to the substrate.

[ASE Threshold] The "ASE threshold" in this specification means when the excitation light is irradiated to the target film to measure the dependence of the excitation light intensity on the emission intensity, and the relationship between the excitation light intensity and the emission intensity is regarded as a linear function, The intensity of the excitation light where the slope changes. Among them, the target thin film may be a light-emitting layer of a current-excited organic semiconductor laser element, or a light-emitting layer of a light-excited organic laser element. In addition, the light-emitting layer may be composed only of the compound represented by the general formula (1), or may include the compound and the host material represented by the general formula (1). For the specific measurement conditions of "ASE threshold", please refer to the column of Examples. For the light-emitting layer of an organic semiconductor laser device, the ASE threshold is preferably 20 μJ/cm ² or less, more preferably 10 μJ/cm ² or less, still more preferably 5 μJ/cm ² or less, particularly preferably 1 μJ/cm ² or less.

[Full amplitude at half peak of luminous wave peak at ASE threshold] In this specification, "the half-peak full amplitude of the luminescence peak at the ASE threshold" means that when the luminescent layer is irradiated with excitation light at an intensity corresponding to the ASE threshold and the luminescence spectrum is observed, among the luminescence peaks appearing in the luminescence spectrum , The full amplitude of the half-peak of the peak of the highest intensity. Among them, for the description of the target film, please refer to the description of the film in the ASE threshold. For the light-emitting layer of the organic semiconductor laser device, the half-peak full amplitude of the light-emitting peak at the ASE threshold is preferably less than 30 nm, more preferably less than 20 nm, and more preferably less than 15 nm.

The organic semiconductor laser device as described above can emit laser light due to the current above the threshold current density flowing between the anode and the cathode. At this time, since the organic semiconductor laser element of the present invention contains the compound represented by the general formula (1), the threshold current density is low. Therefore, the laser light can be emitted at a relatively low current density, and excellent The laser characteristics.

When manufacturing the organic semiconductor laser device of the present invention, the compound represented by the general formula (1) can be used not only in the light-emitting layer, but also in layers other than the light-emitting layer. In this case, the compound represented by general formula (1) used in the light-emitting layer and the compound represented by general formula (1) used in layers other than the light-emitting layer may be the same or different. For example, the compound represented by the general formula (1) can also be used for the injection layer, barrier layer, hole barrier layer, electron barrier layer, exciton barrier layer, hole transport layer, electron transport layer, and the like. The film forming method of these layers is not particularly limited, and can be produced by any process of dry process and wet process. Due to the high stability of the compound represented by the general formula (1), the structure remains stable even in the dry process, and the performance of the structure can be fully demonstrated regardless of the film forming method. [Example]

Examples are listed below to further specifically describe the features of the present invention. The materials, processing contents, processing steps, etc. shown below can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention should not be limitedly illustrated by the specific examples shown below. In addition, the luminescence characteristics were evaluated using a fluorescent spectrophotometer (manufactured by JASCO Corporation: FP-8600), absolute PL quantum yield measuring device (manufactured by Hamamatsu Optical Co., Ltd.: C11347-01), and multi-channel spectrometer (Hamamatsu Optical Co., Ltd.) Manufacturing: PMA-12), fluorescence lifetime measurement device (manufactured by Hamamatsu Kogyo Co., Ltd.: Quantaurus-Tau C11367-03). In addition, the thermal stability was evaluated using a thermogravimetric-differential thermal synchronous measuring device (manufactured by Bruker: TG-DTA 2400SA). Furthermore, a nuclear magnetic resonance device (manufactured by Bruker: AVANCE III 500 MHz spectrometer) and electrochemical measurement (manufactured by BAS: BAS 608D + DPV Electrochemical system) were also used.

[1] Synthesis of Compound (Synthesis Example 1) Synthesis of Compound 1 [Chemical 14]

Under a nitrogen atmosphere, put N,N-dimethylformamide (200 mL) and 3-bromophenol (30.0 g, 174 mmol) in a three-necked flask. After cooling to 0°C in an ice bath, add hydrogenation Sodium (12.8 g, 320 mmol), 1-bromo-2,2-diethoxyethane (31.5 g, 209 mmol) was added dropwise, and the mixture was stirred at 150°C for 5 hours. After the reaction was completed, the reaction liquid was cooled to room temperature, water was added, and extraction was performed with diethyl ether. The organic layer was dried with sodium sulfate, and the solvent was distilled off under reduced pressure. For the residue (reaction product), a mixed solvent of hexane:dichloromethane=1:1 was used as the developing solvent, and the silica gel column chromatography was used to separate and purify the residue (reaction product) to obtain a yield of 42.8 g and a yield of 85.1 % Obtain the transparent oily liquid of Intermediate 1. ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.07-7.15 (m, 3H), 6.84-6.88 (m, 1H), 4.81 (BPBF-1H), 3.98-4.00 (d, J = 5.0 Hz, 2H) , 3.72-3.79 (m, 2H), 3.59-3.63 (m, 2H), 1.25 (t, J = 7.1 Hz, 6H).

[化15]

Put β tin zeolite (catalyst, 4.16 g) in a three-necked flask and replace with nitrogen. Dissolve intermediate 1 (12.0 g, 41.7 mmol) in benzene trifluoride (200 mL) and pour it into the flask. Stir at 112°C for 72 hours. The reaction liquid was filtered, the residue was washed with benzene trifluoride, and the solvent was distilled off the obtained filtrate under reduced pressure. For the residue (reaction product), hexane was used as the developing solvent, and the silica gel column chromatography was used to separate and purify the residue (reaction product) to obtain a transparent oily liquid of intermediate 2 with a yield of 4.24 g and a yield of 52.0%. . ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.71 (s, 1H), 7.62 (d, J = 2.7 Hz, 1H), 7.49 (d, J = 9.6 Hz, 1H), 7.38 (d, J = 2.7 Hz, 1H), 6.76 (d, J = 2.7 Hz, 1H).

[化16]

Intermediate 2 (4.11 g, 20.9 mmol), carbazole (Cz, 5.12 g, 30.6 mmol), palladium acetate (Pd(OAc) ₂ , 0.16 g, 0.713 mmol) and potassium carbonate (3.58 g, 25.9 mmol) were put together In a three-necked flask, after nitrogen substitution, toluene (150 mL) and tri-tert-butylphosphine (0.732 g, 3.62 mmol) were added, and the mixture was stirred at 120°C for 48 hours. Water was added to the reaction liquid, and after extraction with ethyl acetate, the obtained organic layer was dried with sodium sulfate, and the solvent was distilled off under reduced pressure. For the residue (reaction product), a mixed solvent of hexane:dichloromethane=1:1 was used as the developing solvent, and was separated and purified by silica gel column chromatography, so that the yield was 3.66 g and the yield was 61.6. % Obtain the transparent oily liquid of intermediate 3. ¹ H NMR (500 MHz, CDCl ₃ ): δ 8.17 (d, J = 7.9 Hz, 2H), 7.80 (d, J = 8.2 Hz, 1H), 7.76 (d, J = 2.2 Hz, 1H), 7.73 ( s,1H), 7.45 (dd, J = 8.2, 1.9 Hz, 1H), 7.41-7.43 (m, 4H), 7.28-7.32 (m, 2H), 6.91 (dd, J = 2.2 Hz, 1H); ¹³ C NMR (CHCl ₃ ): δ 155.3, 146.3, 141.3, 134.2, 126.9, 125.9, 123.3, 122.4, 122.0, 120.3, 120.0, 110.6, 109.8, 106.7; Anal. Calcd for C ₂₀ H ₁₃ NO: C, 84.78; H, 4.62; N, 4.94. Found: C, 84.65; H, 4.61.

[化17]

Intermediate 3 (0.496 g, 1.75 mmol) was dissolved in tetrahydrofuran (10 mL) and placed in a three-necked flask previously replaced with argon. After cooling to -40°C, n-butyllithium (n-BuLi, 1.6 M, 1.64 mL, 2.63 mmol), stir for 1 hour. A solution obtained by dissolving iodine (0.724 g, 2.85 mmol) in tetrahydrofuran (10 mL) was added dropwise to this mixture, and the mixture was returned to room temperature and further stirred for 12 hours. After adding saturated sodium thiosulfate aqueous solution (20 mL) to the reaction solution, the solvent was distilled off under reduced pressure, and extraction was performed with ethyl acetate. The organic layer was dried with sodium sulfate, and the solvent was distilled off under reduced pressure. The residue (reaction product) was separated and purified by silica gel column chromatography using dichloromethane as a developing solvent to obtain a transparent oily liquid of intermediate 4 with a yield of 0.734 g. ¹ H NMR (500 MHz, CDCl ₃ ): δ 8.16 (s, 1H), 8.15 (t, J = 0.95, 1H) 7.71 (s, 1H) 7.69-7.70 (m, 2H), 7.39-7.45 (m, 4H), 7.28-7.32 (m, 2H), 7.09 (d, J = 0.95 Hz, 1H); ¹³ C NMR (CHCl ₃ ): δ 158.4, 141.1, 134.2, 128.6, 126.0, 123.4, 122.7, 120.4, 120.3 , 120.1, 117.3, 110.0, 110.0, 97.1; Anal. Calcd for C ₂₀ H ₁₂ INO: C, 58.70; H, 2.96; N, 3.42. Found: C, 58.47; H, 2.99; N, 3.25.

[化18]

Place 4,4'-biphenyl diboronic acid (0.169 g, 0.698 mmol) and tetrakis(triphenylphosphine) palladium(0) (Pd(PPh ₃ ) ₄ , 0.226 g, 0.196 mmol) in a two-necked flask After nitrogen replacement, intermediate 4 (0.730 g, 1.78 mmol) was dissolved in toluene (50 mL) and added, and then potassium carbonate (0.436 g, 3.15 mmol) was dissolved in water (50 mL) and added. Reflux for hours. The reaction liquid was filtered, and the residue was washed with dichloromethane and an alkaline aqueous solution, then dissolved in o-dichlorobenzene (30 mL), and heated to 180°C to dissolve it. Methanol was added to the solution, and the precipitated solid was filtered and extracted, thereby obtaining the target compound 1 as a yellow solid with a yield of 0.063 g and a yield of 12.2%. ¹ H NMR (500 MHz, CDCl ₃ ): δ 8.17 (dd, J = 8.5, 1.0 Hz, 4H), 8.04 (d, J = 8.5 Hz, 4H), 7.82-7.84 (m, 6H), 7.72 (s , 2H), 7.47 (dd, J = 10.1, 1.9 Hz, 6H), 7.42-7.46 (m, 4H) 7.29-7.33 (t, 4H), 7.27 (d, J = 0.95 Hz, 2H); Anal. Calcd for C ₅₂ H ₃₂ N ₂ O ₂ : C, 87.13; H, 4.50; N, 3.91. Found: C, 86.86; H, 4.46; N, 3.83.

(Synthesis Example 2) Synthesis of Compound 2 [Chemical Formula 19]

Intermediate 2 (1.03 g, 5.26 mmol), bis(pinacol ester) diborane (B ₂ pin ₂ , 0.645 g, 2.54 mmol), bis(diphenyl) obtained by the same procedure as Synthesis Example 1 Phosphine) ferrocene] dichloropalladium (II) (PdCl ₂ (dppf), 0.150 g, 0.205 mmol), potassium carbonate (2.13 g, 15.4 mmol) are placed in a two-necked flask, after nitrogen replacement, add two Methyl sulfoxide (30 mL), stirred at 80°C for 24 hours. The reaction liquid was cooled to room temperature, water was added, and the precipitate was filtered and extracted. For the precipitate, a mixed solvent of hexane: dichloromethane = 9:1 was used as the developing solvent, and was separated and purified by silica gel column chromatography, thereby obtaining an intermediate with a yield of 0.379 g and a yield of 62.0% 5 is a colorless solid. ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.78 (s, 2H), 7.65–7.67 (m, 4H), 7.55 (dd, J = 8.2, 1.6 Hz, 2H), 6.81 (dd, J = 1.1 Hz , 2H); ¹³ C NMR (CHCl ₃ ): δ 155.8, 145.6, 138.3, 126.7, 122.8, 121.4, 110.3, 106.6; Anal. Calcd for C ₁₆ H ₁₀ O ₂ : C, 82.04; H, 4.30. Found: C, 81.97; H, 4.46.

[化20]

Intermediate 5 (0.315 g, 1.35 mmol) was dissolved in tetrahydrofuran (10 mL) and placed in a three-necked flask previously replaced with argon. After cooling to -40°C, n-butyllithium (n-BuLi, 1.6 M, 2.80 mL, 4.34 mmol), stir for 1 hour. A solution obtained by dissolving iodine (1.03 g, 4.06 mmol) in tetrahydrofuran (10 mL) was added dropwise to this mixture, and the mixture was returned to room temperature and further stirred for 12 hours. After adding saturated sodium thiosulfate aqueous solution (20 mL) to the reaction solution, the solvent was distilled off under reduced pressure, and extraction was performed with ethyl acetate. The organic layer was dried with sodium sulfate, and the solvent was distilled off under reduced pressure. For the residue (reaction product), dichloromethane was used as the developing solvent, and the silica gel column chromatography was used to separate and refine the colorless solid of Intermediate 6 with a yield of 0.506 g and a yield of 77.5%. ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.70 (s, 2 H), 7.57 (d, J = 8.2, 2H), 7.49 (dd, J = 8.2, 1.6 Hz, 2H), 6.99 (d, J = 0.95 Hz, 2H); ¹³ C NMR (CHCl ₃ ): δ 161.6, 140.4, 131.2, 125.7, 122.6, 119.9, 112.3, 99.0.

[化21]

Place 4-(9H-carbazol-9-yl)phenylboronic acid (1.06 g, 3.69 mmol), tetrakis(triphenylphosphine) palladium(0) (Pd(PPh ₃ ) ₄ , 0.124 g, 0.107 mmol) in In a two-neck flask, after nitrogen replacement, Intermediate 6 (0.510 g, 1.04 mmol) was dissolved in toluene (50 mL) and added, and potassium carbonate (1.20 g, 8.68 mmol) was dissolved in water (50 mL). Add and reflux for 48 hours. The reaction liquid was filtered, and the residue was washed with dichloromethane and an alkaline aqueous solution, then dissolved in o-dichlorobenzene (30 mL), and heated to 180°C to dissolve it. The solution was filtered to remove the catalyst, methanol was added, and the precipitated solid was filtered and extracted, thereby obtaining the target compound 2 as a yellow solid with a yield of 0.464 g and a yield of 62.2%. ¹ H NMR (500 MHz, CDCl ₃ ): δ 8.17 (d, J = 8.5, 8H), 7.92 (s, 2H), 7.71-7.77 (m, 6H), 7.67 (dd, J = 8.2, 1.6 Hz, 2H), 7.52 (d, J = 8.2 Hz, 4H), 7.43-7.47 (m, 4H) 7.30-7.33 (m, 4H), 7.24 (d, J = 0.63 Hz, 2H); ¹³ C NMR (CHCl ₃ ): δ 155.8, 140.6, 138.2, 137.8, 129.3, 128.5, 127.3, 126.3, 126.0, 123.5, 122.9, 121.3, 120.3, 120.1, 109.8, 109.6, 101.9; Anal.Calcd for C ₅₂ H ₃₂ N ₂ O ₂ : C, 87.13; H, 4.50; N, 3.91. Found: C, 86.99; H, 4.51; N, 3.67.

[2] Evaluation The stability and luminescence characteristics of each compound synthesized and the following BSB-Cz (comparative compound) were evaluated. [化22]

(Evaluation of stability) For compounds 1, 2 and BSB-Cz, a vapor-deposited film was formed by a vacuum vapor deposition method with a vacuum of 10 ^-4 to 10 ^-5 Pa, then melted, and then analyzed by NMR . Also, unlike this, after subliming the compounds 1, 2 and BSB-Cz, respectively, NMR analysis was performed. Among them, because the pressure in the sublimation device is higher than the pressure in the vacuum evaporation device, the sublimation temperature is higher than the evaporation temperature of the vacuum evaporation method. NMR analysis was performed. As a result, in the case of BSB-Cz, in the NMR spectrum measured after the vapor deposition film was melted, small peaks not seen in the NMR spectrum before vacuum vapor deposition were observed, and it was confirmed that impurities were generated. In addition, in the NMR spectrum measured after sublimation, new impurity peaks were observed, and the peaks derived from phenylcarbazole were also confirmed. It can be seen that BSB-Cz generates impurities through thermal processes such as vacuum evaporation or sublimation, especially in the case of sublimation, the decomposition proceeds sufficiently. On the other hand, in the case of Compounds 1 and 2, the NMR spectrum measured after melting or sublimation of the vapor-deposited film confirms that there is no peak derived from the decomposition product, and decomposition is suppressed. In addition, for compounds 1, 2 and BSB-Cz, thermogravimetric measurement (TG) at 1 Pa and thermogravimetric-differential thermal measurement (TG-DTA) at 1 atm were performed. As a result, although the sublimation temperature was the same, However, the decomposition temperature of BSB-Cz is 478°C. In contrast, the decomposition temperature of compound 1 is 539°C, and the decomposition temperature of compound 2 is 543°C, showing a higher decomposition temperature. From the above results, it can be confirmed that compounds 1 and 2 have particularly higher thermal stability than BSB-Cz.

(Evaluation of PL luminescence characteristics and electrochemical characteristics of the solution) Compounds 1, 2 and BSB-Cz were dissolved in toluene, chloroform or N,N-dimethylformamide to prepare 9 solutions. At this time, the concentration of each solution is set to 10 ^-5 M. For each solution prepared, the absorption spectrum and the luminescence characteristics under 340 nm excitation light were investigated. Table 1 shows the measurement results of luminescence characteristics. Among them, the photoluminescence quantum yield (PL quantum yield Φ _PL ) and luminescence lifetime T represent both the value measured under the atmosphere (in air) and the value measured under the nitrogen atmosphere (in N ₂ ) .

[Table 1] Compound No Solvent Maximum emission wavelength λ _max (nm) PL quantum yieldΦ _PL in air(%) PL quantum yieldΦ _PL in N ₂ (%) Luminous lifetime T in air(ns) Luminous lifetime T in N ₂ (ns) k _r ×10 ⁸ (s ^-1 ) Compound 1 Toluene 419 94 96 0.93 0.97 9.9 Chloroform 423 89 96 1.0 1.1 8.9 N,N-Dimethylformamide 447 94 98 1.4 1.4 6.8 Compound 2 Toluene 407 94 96 0.89 0.93 10 Chloroform 407 94 96 0.95 0.99 9.7 N,N-Dimethylformamide 409 96 100 1.02 1.04 9.6 BSB-Cz Toluene 420 83 89 0.84 0.87 10 Chloroform 423 86 88 0.93 0.95 9.3 N,N-Dimethylformamide 446 90 96 1.1 1.1 8.5

The absorption spectra, luminescence lifetime T and emission rate constant kr of the solutions of Compound 1, 2 and BSB-Cz are very consistent. Among them, the emission rate constant kr is related to the ASE oscillation threshold. Therefore, according to the results, compounds 1 and 2 exhibit the same low ASE oscillation threshold as BSB-Cz. In addition, regarding the emission peak, the greater the polarity of the solvent for any compound (in the order of N,N-dimethylformamide, chloroform, and toluene), the more it shifts to the longer wavelength side, and the degree of shift is the same. In the same situation, the maximum emission wavelengths of each other are approximately the same. On the other hand, with regard to the photoluminescence quantum yield, the solutions of Compounds 1 and 2 showed higher values than the BSB-Cz solution. From this, it can be seen that Compounds 1 and 2 maintain the same luminescence characteristics as BSB-Cz, improve stability and quantum yield, and are improved as luminescent materials.

In addition, compound 1 and BSB-Cz were dissolved in dichloromethane, respectively, and the electrochemical characteristics were measured by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The results are shown in Table 2. The values in Table 2 are calculated by setting the half-wave potential of the reference material ferrocene to 0, HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital, the lowest unoccupied molecular orbital) The energy levels of) are calculated from the oxidation potential and reduction potential measured by CV.

[Table 2] Compound No CV DPV HOMO(eV) LUMO(eV) Redox potential Eg ^redox (eV) Optical band gap Eg ^opt (eV) Oxidation potential E _ox (V) Reduction potential E _red (V) Oxidation potential E _ox (V) Reduction potential E _red (V) Compound 1 0.77 -2.15 0.71 -2.39 -5.6 -2.7 2.92 2.93 BSB-Cz 0.78 -2.10 0.72 -2.40 -5.6 -2.7 2.88 2.93

As shown in Table 2, the oxidation potential and reduction potential of compound 1 and BSB-Cz are similar, and the energy levels of HOMO and LUMO are also similar.

(Evaluation of PL luminescence characteristics of a single film) A thin film of compound 2 (a single film) with a thickness of 100 nm was formed on a quartz substrate by a vacuum evaporation method under a vacuum of 10 ^-4 Pa or less. Furthermore, under the same conditions, a thin film of BSB-Cz (individual film) was formed with a thickness of 100 nm on the quartz substrate. For each of the formed thin films, the surface roughness by atomic force microscope and the crystallinity by X-ray diffraction analysis were evaluated. As a result, it was found that the surface roughness was low, and they were all amorphous. In addition, for each individual film, the luminescence characteristics under 340 nm excitation light were measured. As a result, the maximum wavelength λ _max of the single film system of BSB-Cz was 480 nm, and the PL quantum yield under the atmosphere Φ _PL was 69%. The light-emitting lifetime T is 1.6 ns and the emission rate constant k _r is 4.4×10 ⁸ s ^-1 . In addition, the maximum wavelength λ _max of the single film of compound 2 is 452 nm, the PL quantum yield Φ _PL under the atmosphere is 79%, the PL quantum yield Φ _PL under the nitrogen atmosphere is 87%, and the luminescence lifetime under the atmosphere T The luminescence lifetime T under nitrogen atmosphere is 1.8 ns, and the emission rate constant k _r is 4.7×10 ⁸ s ^-1 . It can be seen that the PL quantum yield and emission rate constant are higher than BSB-Cz, and the luminescence characteristics are improved.

(Evaluation of light durability of single film) For the single film of compound 2 and the single film of BSB-Cz produced under the same conditions as those used in the evaluation of PL luminescence characteristics, continuous irradiation of 405 nm from a CW (continuous wave) laser light source with an intensity of 18 μW Excite the light and investigate the time-dependent change of its luminous intensity. The results are shown in Fig. 2. Furthermore, the intensity of irradiation is adjusted so that the density of excitons in each thin film is equal. As shown in Figure 2, in the case of a single film of Compound 2, the luminous intensity remains constant during the excitation light irradiation period. In contrast, in the case of a single film of BSB-Cz, the luminous intensity decreases with time. It can be seen that, compared with BSB-Cz, compound 2 has higher stability (light durability) in the excited state, and is suitable as a compound for laser materials whose exciton density is inevitably higher.

(Evaluation of PL luminescence characteristics of doped film) Co-evaporate compound 2 and CBP (4,4') from different evaporation sources on quartz substrate by vacuum evaporation method under the condition of vacuum degree below 10 ^-4 Pa -Bis(N-carbazolyl)-1,1'-biphenyl, 4,4'-bis(N-carbazolyl) biphenyl), with a thickness of 130 nm to form a thin film of compound 2 with a concentration of 6.0% by weight (doped Miscellaneous film). In addition, under the same conditions, BSB-Cz and CBP were co-evaporated from different evaporation sources on the quartz substrate to form a thin film (doped film) with a BSB-Cz concentration of 6.0 wt% with a thickness of 130 nm. For each doped film, the luminescence characteristics under 340 nm excitation light were measured. As a result, the maximum wavelength λ _max of the doped film of BSB-Cz was 462 nm, and the PL quantum yield under the atmosphere Φ _PL was 87%. The light-emitting lifetime T is 1.1 ns, and the emission rate constant k _r is 7.9×10 ⁸ s ^-1 . In addition, the maximum wavelength λ _max of the doped film of compound 2 is 445 nm, the PL quantum yield Φ _PL under the atmosphere and nitrogen atmosphere are both 100%, the luminescence lifetime T under the atmosphere is 1.3 ns, The emission lifetime T is 1.6 ns, and the emission rate constant k _r is 7.6×10 ⁸ s ^-1 , which shows a higher quantum yield than the doped film of BSB-Cz.

(Evaluation of ASE emission characteristics of doped film) For the doped film of compound 2 and the doped film of BSB-Cz produced under the same conditions as those used in the evaluation of PL emission characteristics, investigate the 337 nm of nitrogen laser Luminescence characteristics of ASE under excitation light. For the doped film of Compound 2, the results obtained by measuring the excitation intensity dependence of the luminescence intensity and the full-width FWHM of the luminescence peak are shown in FIG. 3, and the PL spectrum and the ASE spectrum are shown in FIG. 4. The PL spectrum is the luminescence spectrum measured at an excitation intensity of 0.7 μJ/cm ² . For the BSB-Cz doped film, the results obtained by measuring the excitation intensity dependence of the luminescence intensity and the FWHM of the luminescence peak half-peak full-width FWHM are shown in FIG. 5, and the PL spectrum and the ASE spectrum are shown in FIG. 6. The PL spectrum is the luminescence spectrum measured under an excitation intensity of 0.2 μJ/cm ² , and the ASE spectrum is the luminescence spectrum measured under an excitation intensity of 15 μJ/cm ² . As shown in Figures 3 and 5, for any doped film, in the excitation intensity dependence graph of luminescence intensity, confirm the change point (threshold value E _th ) of the slope change, and confirm that the FWHM is narrowed depending on the excitation intensity的 related relationship. In addition, as shown in Figs. 4 and 6, at an excitation intensity above the threshold E _th , a sudden emission peak that can be confirmed as an ASE peak is observed. Among them, it can be seen from the measurement results that the maximum wavelength λ _ASE of the ASE of the doped film of BSB-Cz is 458 nm, the ASE threshold E _th is 0.89 μJ/cm ² , and the maximum wavelength λ of the ASE of the doped film of Compound 2 _{The ASE} is 442 nm, and the ASE threshold E _th is 0.90 μJ/cm ² , which is equivalent to the BSB-Cz doped film. From the above results, it can be seen that the compound represented by the general formula (1) is the same as BSB-Cz and is a compound capable of emitting ASE. Furthermore, the quantum yield and stability are higher than that of BSB-Cz, which is a more excellent luminescent material.

(Evaluation of durability of single film during ASE oscillation) For the single film of compound 1, the single film of compound 2, and the single film of BSB-Cz produced under the same conditions as those used in the evaluation of PL luminescence characteristics, use The same excitation light source (337 nm, pulse width 0.8 ns, 10 Hz) used in the evaluation of ASE luminescence characteristics was irradiated with an intensity of 950 μJ/cm ² sufficiently higher than the ASE oscillation threshold. The investigation was conducted under a nitrogen atmosphere. The luminous intensity changes over time. The results are shown in Fig. 7. In addition, the horizontal axis represents the measurement time. As shown in Figure 7, the reduction of the luminous intensity of the individual films of Compound 1 and Compound 2 is smaller than the reduction of the luminous intensity of the individual films of BSB-Cz. It can be seen that, compared with BSB-Cz, compound 1 and compound 2 have higher stability (light durability) even in the laser oscillation state, and are suitable as compounds for laser materials.

[產業上之可利用性][化23]

[Industrial availability]

The compound of the present invention exhibits a higher quantum yield and a lower ASE threshold, and the stability is also higher. Therefore, by using the compound of the present invention as a light-emitting material of an organic semiconductor laser device, an organic semiconductor laser device with a lower laser oscillation threshold can be realized. Therefore, the industrial applicability of the present invention is high.

1: substrate 2: anode 3: hole injection layer 4: hole transport layer 5: Light-emitting layer 6: Electron transport layer 7: Cathode

Fig. 1 is a schematic cross-sectional view showing an example of the layer structure of the organic semiconductor laser element of the present invention. Figure 2 is a graph showing the light tolerance of Compound 2 and BSB-Cz. Fig. 3 is a graph showing the dependence of the luminous intensity of a single film of compound 2 on the excitation light intensity and the full width at half maximum (FWHM) of the peak. Figure 4 shows the PL (photoluminescence) spectra and ASE spectra of a single film of Compound 2. Fig. 5 is a graph showing the dependence of the luminous intensity of a single film of BSB-Cz and the FWHM of the excitation light intensity. Figure 6 shows the PL spectrum and ASE spectrum of a single film of BSB-Cz. Fig. 7 is a graph showing the durability of each individual film of Compound 1, Compound 2, and BSB-Cz during ASE oscillation.

Claims (13)

A compound represented by the following general formula (1), General formula (1) Z ¹ -LZ ² [In the general formula (1), Z ¹ and Z ² each independently represent substituted or unsubstituted The two aryl groups constituting the above-mentioned diarylamino group are directly bonded to each other or via a linking group. L represents a conjugated linking group containing a benzofuran structure, which is used to connect Z ¹ and Z ² The link chain contains more than 5 rings]. The compound of claim 1, wherein the above-mentioned conjugated system linking group has a group selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted furan ring, a substituted or unsubstituted heteroaromatic ring, and a A structure in which two or more of the substituted or unsubstituted vinylidene groups are connected (wherein, the benzene ring and the furan ring may be condensed, and the furan ring and the heteroaromatic ring may be condensed). The compound of claim 1, wherein the above-mentioned conjugated linking group comprises a substituted or unsubstituted benzofuran-2,6-diyl group. The compound of claim 1, wherein the above-mentioned conjugated linking group has a structure in which one or more groups selected from the following group A are connected, [化1]

[The hydrogen atom in each group of the above group A may be substituted, * indicates the linking position, and at least one group containing a benzofuran structure is selected from the above group A, and the group A includes a benzofuran structure At least one of the atoms constituting the benzene ring of the benzene ring of the group and the group containing the fluorine structure may be substituted by a nitrogen atom]. The compound of claim 1, wherein the above-mentioned conjugated linking group includes a group represented by the following general formula (2), [化2]

[In the general formula (2), R ¹ and R ² are bonded to each other to form -O-, R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, or are bonded to each other to form a linking group, * represents a link Position, the hydrogen atom bonded to the benzene ring in the general formula (2) can be substituted by a substituent]. The compound according to any one of claims 1 to 5, wherein the chain length of the conjugated linking group is 10-30. The compound of any one of claims 1 to 5, wherein Z ¹ and Z ² are each independently a group represented by the following general formula (3), [化3]

[In the general formula (3), R ¹¹ to R ²⁰ each independently represent a hydrogen atom or a substituent, R ¹⁵ and R ¹⁶ are bonded to each other to form a single bond or a linking group, R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ can be bonded to each other to form a cyclic structure, * represents a bond End position]. The compound of any one of claims 1 to 5, wherein Z ¹ and Z ² are each independently a group represented by any one of the following general formulas (4) to (8), [formation 4]

[In the general formulae (4) to (8), R ²¹ to R ²⁴ , R ²⁷ to R ³⁸ , R ⁴¹ to R ⁴⁸ , R ⁵¹ to R ⁵⁸ , R ⁶¹ to R ⁶⁵ , and R ⁸¹ to R ⁹⁰ are each independent Ground represents a hydrogen atom or a substituent, R ²¹ and R ²² , R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ and R ⁴⁴ , R ⁴⁵ And R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ , R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ , R ⁵⁷ and R ⁵⁸ , R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶³ and R ⁶⁴ , R ⁶⁴ and R ⁶⁵ , R ⁵⁴ and R ⁶¹ , R ⁵⁵ and R ⁶⁵ , R ⁸¹ and R ⁸² , R ⁸² and R ⁸³ , R ⁸³ and R ⁸⁴ , R ⁸⁵ and R ⁸⁶ , R ⁸⁶ and R ⁸⁷ , R ⁸⁷ and R ⁸⁸ , R ⁸⁹ and R ⁹⁰ can be bonded to each other to form a cyclic structure, and * indicates bonding position]. The compound of claim 8, wherein Z ¹ and Z ² are each independently a group represented by the above general formula (4). A use of the compound according to any one of claims 1 to 9, which is used as a luminescent material. The use as a luminescent material according to claim 10, wherein the above-mentioned compound is a compound that emits spontaneously emitting amplified light. If claim 10 or 11 is used as a luminescent material, it is used as a luminescent material for an organic semiconductor laser element. An organic semiconductor laser element comprising a compound represented by the following general formula (1), the general formula (1) Z ¹ -LZ ² [In the general formula (1), Z ¹ and Z ² are each independently represented In the substituted or unsubstituted diarylamino group, the two aryl groups constituting the above-mentioned diarylamino group are bonded to each other directly or via a linking group, and L represents a conjugated linking group containing a benzofuran structure].

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