Organic solid-state lasers, compounds, and uses thereof

Abstract

The compound represented by the following formula has excellent laser oscillation properties: G 1 and G 2 represents H or a substituent, and SP 1 and SP 2 represents benzofurylene, dibenzofurylene, etc., and Q 1 and Q 2 represent H, alkyl, alkoxy, or halogen, or are joined together to form JPEG2025540851000071.jpg25170 or (In the formula, G 3 and G 4 represents H, aryl, etc.) JPEG2025540851000072.jpg33170

Description

[Technical Field]

[0001] The present invention relates to organic solid state lasers, novel compounds, and the use of the compounds as emitters in organic solid state lasers. [Background technology]

[0002] Research into developing organic solid-state lasers with low laser oscillation thresholds is actively underway. To realize such organic solid-state lasers, it is necessary to develop organic compounds with excellent laser oscillation characteristics. To this end, various organic compounds have been synthesized, and their laser oscillation characteristics have been investigated. Non-Patent Document 1 reports that bis-stilbene derivatives such as BSBCz exhibit low ASE thresholds and are excellent organic laser materials. However, the number of useful organic laser materials remains limited. For example, efficient and useful organic laser materials emitting in the infrared region above 650 nm have yet to be developed. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Applied Physics Letters (Appl. Phys. Lett.) 2005, 86, 071110 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a new light-emitting organic laser material and an organic solid-state laser using this material. [Means for solving the problem]

[0005] As a result of extensive research, the present inventors have found that a group of compounds having a specific structure have excellent laser oscillation properties. Thus, the present inventors have provided the following invention:

[0006] [1]The following formula (1): Formula (1) [ka] (In the formula, G 1 and G 2 each independently represents a hydrogen atom or a substituent, SP 1 represents a linking group represented by one of the following formulas (2) and (4) to (7), and SP 2 represents a linking group represented by one of the following formulas (3) to (7): [ka] (In the formula, R 1 ~R 32 each independently represents a hydrogen atom or a substituent, and X 1 ~X 6 are each independently a sulfur atom, an oxygen atom, or NT 1 where T 1 represents a substituted or unsubstituted alkyl group, and each * represents the binding site), n is an integer equal to or greater than 1, m is an integer equal to or greater than 1, Q 1 and Q 2 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a halogen atom, or Q 1 and Q 2 are joined together, [ka] (In the formula, G 3 and G 4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group; and * represents the bonding site to the benzene ring of formula (1)) forms a compound represented by.

[0007] [2]Q 1 and Q 2 are joined together, [ka] and the compound has the formula [ka] The compound according to [1], having a structure represented by:

[0008] [3]Q 1 and Q 2 are joined together, [ka] and the compound has the formula [ka] The compound according to [1], having a structure represented by:

[0009] [4] SP 1 The compound according to any one of [1] to [3], which is represented by formula (2):

[0010] [5] SP 1 is expressed by equation (2), and SP 2 The compound according to any one of [1] to [3], which is represented by formula (3):

[0011] [6]SP 1 The compound according to any one of [1] to [3], which is represented by formula (4):

[0012] [7]SP 1 and SP 2 The compound according to any one of [1] to [3], which is represented by formula (4):

[0013] [8]SP 1The compound according to any one of [1] to [3], which is represented by formula (5):

[0014] [9]SP 1 and SP 2 The compound according to any one of [1] to [3], which is represented by formula (5):

[0015]

[10] SP 1 The compound according to any one of [1] to [3], which is represented by formula (6):

[0016]

[11] SP 1 is expressed by equation (6), and SP 2 The compound according to any one of [1] to [3], which is represented by formula (7):

[0017]

[12] SP 1 The compound according to any one of [1] to [3], which is represented by formula (7):

[0018]

[13] SP 1 is expressed by equation (7), and SP 2 The compound according to any one of [1] to [3], which is represented by formula (6):

[0019]

[14] SP 1 is expressed by equation (2), and SP 2 The compound according to any one of [1] to [3], which is represented by formula (4):

[0020]

[15] SP 1 is expressed by equation (2), and SP 2 The compound according to any one of [1] to [3], which is represented by formula (5):

[0021]

[16] SP 1 is expressed by equation (2), and SP 2 The compound according to any one of [1] to [3], which is represented by formula (6):

[0022]

[17] SP 1 is expressed by equation (2), and SP 2 The compound according to any one of [1] to [3], which is represented by formula (7):

[0023]

[18] X 1 ~X 6 The compound according to any one of [1] to

[17] , wherein is an oxygen atom.

[0024]

[19] X 1 ~X 6 The compound according to any one of [1] to

[17] , wherein is a sulfur atom.

[0025]

[20] The compound according to any one of [1] to

[19] , wherein m and n are 1.

[0026]

[21] G 1 and G 2 The compound according to any one of [1] to

[20] , wherein is a hydrogen atom.

[0027]

[22] G 1 and G 2 and each independently represent a substituted or unsubstituted diarylamino group.

[0028]

[23] G 1 and G 2 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted carbazolyl group.

[0029]

[24] G 3 and G 4 The compound according to any one of [1] to

[23] , wherein is a hydrogen atom.

[0030]

[25] G 3 and G 4are each independently a substituted or unsubstituted aryl group.

[0031]

[26] R 1 and R 32 The compound according to any one of [1] to

[25] , wherein is a hydrogen atom.

[0032]

[27] The compound according to any one of [1] to

[26] , which has a symmetric structure.

[0033]

[28] [ka] The compound according to [1], selected from:

[0034]

[29] An organic solid-state laser comprising the compound according to any one of [1] to

[28] .

[0035]

[30] An organic electroluminescent device comprising the compound according to any one of [1] to

[28] . [Effects of the Invention]

[0036] The compound represented by formula (1) has excellent laser oscillation properties. Organic solid-state lasers containing the compound of formula (1) exhibit low laser oscillation thresholds and high luminous efficiencies. [Brief explanation of the drawings]

[0037] [Figure 1] FIG. 1 shows the emission spectrum after the ASE threshold of a blend coating of CBP and Compound 1 (Example 2). [Figure 2] FIG. 1 shows a graph of output light intensity (left vertical axis) and full width at half maximum (right vertical axis) emitted from a blend coating of CBP and Compound 1 versus excitation intensity (Example 2). [Figure 3] FIG. 1 shows an OLED device structure of Example 3. [Figure 4]FIG. 1 shows the emission spectrum after the ASE threshold of a blend coating of CBP and Compound 2 (Example 4). [Figure 5] FIG. 1 shows a graph of output light intensity (left vertical axis) and full width at half maximum (right vertical axis) emitted from a blend coating of CBP and Compound 2 versus excitation intensity (Example 5). DETAILED DESCRIPTION OF THE INVENTION

[0038] The present invention will be described in detail below. Elements of the present invention may be described below with reference to representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and examples. In this specification, a numerical range expressed based on an upper limit and / or a lower limit means a range that includes the upper limit and / or the lower limit. For example, room temperature means 25°C.

[0039] definition The hydrogen atoms present in the compounds used in the present invention are not particularly limited in isotope species. For example, all hydrogen atoms in the molecule are 1 H, all or part of which may be 2 It may be H (deuterium (D)).

[0040] The alkyl group referred to in this application may be linear, branched, or cyclic, and linear or branched alkyl groups can be used. Unless otherwise specified, the alkyl group has 1 to 40 carbon atoms, for example, 1 to 30 carbon atoms, for example, 1 to 20 carbon atoms, for example, 1 to 12 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl), for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. The alkyl group may be an acyclic group. The alkyl group may be a cyclic group. Examples of cyclic alkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.1.1]hexyl, and bicyclo[2.2.1]heptyl. The alkyl group may be substituted or unsubstituted. Examples of substituents in this case include alkoxy, aryl, aryloxy, acyl, hydroxyl, halogen atoms, nitro, diarylamino (including carbazol-9-yl), cyano, and combinations thereof. For example, alkoxy, aryl, aryloxy, and combinations thereof may be used.

[0041] The aryl group referred to in this application may have a structure containing only one aromatic ring, or may have a structure containing two or more aromatic rings fused together. Unless otherwise specified, the aryl group has 6 to 22 ring-forming carbon atoms, for example, 6 to 18 ring-forming carbon atoms, for example, 6 to 14 ring-forming carbon atoms, for example, 6 to 10 ring-forming carbon atoms. Examples of aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthranyl, 2-anthranyl, 9-anthranyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-naphthacenyl, 2-naphthacenyl, 1-pyrenyl, and 2-pyrenyl. The aryl group may be substituted or unsubstituted. In this case, examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group, a hydroxyl group, a halogen atom, a nitro group, a diarylamino group (including a carbazol-9-yl group), a cyano group, and combinations thereof. For example, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a diarylamino group (including a carbazol-9-yl group), and combinations thereof can be used.

[0042] The heteroaryl group referred to in this application may have a structure containing only one heteroaromatic ring, or may have a structure containing two or more heteroaromatic rings fused together. The heteroaryl group may contain at least one heteroaromatic ring and at least one aromatic ring. Unless otherwise specified, the heteroaryl group has 5 to 22 ring-forming atoms, for example, 5 to 18 ring-forming atoms, for example, 5 to 14 ring-forming atoms, for example, 5 to 10 ring-forming atoms. Examples of heteroaryl groups include 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 1-isoquinolyl, and 3-isoquinolyl. Other examples of heteroaryl groups include benzofuryl, pyrrolyl, indolyl, isoindolyl, azaindolyl, benzothienyl, pyridyl, quinolinyl, isoquinolyl, imidazolyl, benzimidazolyl, pyrazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, isothiazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, cinnolinyl, phthalazinyl, quinazolinyl, carbazol-1-yl, carbazol-2-yl, carbazol-3-yl, and carbazol-4-yl groups, for example, carbazol-1-yl, carbazol-2-yl, carbazol-3-yl, and carbazol-4-yl groups can be used. Heteroaryl groups can be substituted or unsubstituted. In this case, examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, a halogen atom, a nitro group, a diarylamino group (including a carbazol-9-yl group), a cyano group, and combinations thereof. For example, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and combinations thereof can be used.

[0043] The diarylamino group referred to in this application may have a structure in which the two aryl groups constituting the diarylamino group are not bonded to each other. The diarylamino group referred to in this application may have a structure in which the two aryl groups constituting the diarylamino group are bonded to each other via a single bond or a linking group, and the heteroaryl group referred to in this application does not include such types of diarylamino groups. Examples of linking groups include -O-, -S-, -N(CH3)2-, -N(CH5)2-, -CH2-, -C(CH3)2-, and -C(CH5)2-. For example, the diarylamino group is a substituted or unsubstituted carbazol-9-yl group.

[0044] The alkenyl group referred to in the present application may be linear, branched, or cyclic; for example, linear or branched alkenyl groups can be used. Unless otherwise specified, the alkenyl group has 2 to 40 carbon atoms, for example, 2 to 30 carbon atoms, for example, 2 to 20 carbon atoms, for example, 2 to 12 carbon atoms (e.g., ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, n-pentenyl, isopentenyl, n-hexenyl, isohexenyl, and 2-ethylhexenyl). The alkenyl group as a substituent may be further substituted with a substituent. For the substituent, reference can be made to the description of the substituent for the alkyl group.

[0045] The alkynyl group referred to in the present application may be linear or branched, and for example, a linear alkynyl group can be used. Unless otherwise specified, the alkynyl group has 2 to 40 carbon atoms, for example, 2 to 30 carbon atoms, for example, 2 to 20 carbon atoms, for example, 2 to 12 carbon atoms. The alkynyl group as a substituent may be further substituted with a substituent. For the substituent, reference can be made to the description of the substituent for the alkyl group.

[0046] With regard to the alkyl moieties of the alkoxy groups and dialkylamino groups referred to in this application, reference can be made to the descriptions of the alkyl groups.

[0047] With regard to the aryl moieties of the aryloxy group and diarylamino group referred to in this application, reference can be made to the description of the aryl group.

[0048] With regard to the heteroaryl moiety of the heteroaryloxy group referred to in this application, reference can be made to the description of the heteroaryl group.

[0049] A halogen atom referred to in this application is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0050] A compound represented by formula (1) The compound of the present invention has the following formula (1): Formula (1) [ka] It has a structure represented by:

[0051] G in Equation (1) 1 and G 2 each independently represents a hydrogen atom or a substituent. 1 and G 2 is a hydrogen atom. 1 and G 2 are each independently a substituent, e.g., a substituent that can stabilize a molecule. 1 and G 2Examples of the substituent include substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted heteroaryloxy groups, substituted or unsubstituted diarylamino groups, substituted or unsubstituted dialkylamino groups, substituted or unsubstituted alkenyl groups, and substituted or unsubstituted alkynyl groups, such as substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted heteroaryl groups, and substituted or unsubstituted diarylamino groups. In some embodiments, the substituent is a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkyloxy group, such as a substituted or unsubstituted alkyl group. In some embodiments, the substituent is a substituted or unsubstituted aryl group or a substituted or unsubstituted aryloxy group, such as a substituted or unsubstituted aryl group, including a substituted or unsubstituted diarylaminophenyl group, and a substituted or unsubstituted dialkylamino group. In some embodiments, the substituent is a substituted or unsubstituted carbazolyl group, such as a substituted or unsubstituted carbazol-1-yl, carbazol-2-yl, carbazol-3-yl, or carbazol-4-yl group, or, for example, a substituted or unsubstituted carbazol-9-yl group.

[0052] G 1 and G 2 Specific examples of groups representing the formula are shown below. However, the G 1 and G 2 The group represented by is not limited to the following specific examples. * -CH3 and * In specific examples other than -OCH3, the CH3 symbol is omitted in the case of a methyl group. * SP 1 or SP 2 represents the binding site for

[0053] [ka]

[0054] [ka]

[0055] The hydrogen atoms in each structure may be replaced by substituents such as groups selected from alkyl groups, alkoxy groups, aryl groups, aryloxy groups, and combinations thereof.

[0056] G in Equation (1) 1 and G 2 may be the same or different from each other. For example, G 1 and G 2 is the same.

[0057] SP in Eq. (1) 1 represents a linking group represented by one of the following formulas (2) and (4) to (7). 2 represents a linking group represented by one of the following formulas (3) to (7).

[0058] [ka]

[0059] R in Equations (2) to (7) 1 ~R 32 each independently represents a hydrogen atom or a substituent. 1 ~R 32 is a hydrogen atom. In some embodiments, R 1 ~R 4 at least one of R is a substituent; 5 ~R 8 at least one of R is a substituent; 9 ~R 14 at least one of R is a substituent; 15 ~R 20 at least one of R is a substituent; 21 ~R 26 at least one of is a substituent, and R27 ~R 32 At least one of R is a substituent. 1 ~R 32 Regarding the substituents for G 1 and G 2 The description of the substituents for the above can be referred to.

[0060] For example, G 1 If is a hydrogen atom, G 1 SP bound to 1 R in 1 ~R 3 , R 9 ~R 11 , R 15 ~R 17 , R 21 ~R 23 , and R 27 ~R 29 is also a hydrogen atom. For example, G 1 SP bound to 1 R in 1 ~R 3 , R 9 ~R 11 , R 15 ~R 17 , R 21 ~R 23 , and R 27 ~R 29 When at least one of is a substituent, G 1 is a substituent. For example, G 2 If is a hydrogen atom, G 2 SP bound to 2 R in 6 ~R 8 , R 12 ~R 14 , R 18 ~R 20 , R 24 ~R 26 , and R 30 ~R 32 is also a hydrogen atom. For example, G 2 SP bound to 2 R in 6 ~R 8 , R 12 ~R 14 , R 18 ~R 20 , R24 ~R 26 , and R 30 ~R 32 When at least one of is a substituent, G 2 is a substituent.

[0061] X in formulas (2) to (7) 1 ~X 6 are each independently a sulfur atom, an oxygen atom, or NT 1 where T 1 represents a substituted or unsubstituted alkyl group, and each * represents a binding site. For example, a sulfur atom or an oxygen atom can be used, for example, an oxygen atom can be used.

[0062] n is an integer of 1 or greater, for example, an integer of 1 to 3, for example, 1 or 2, for example, 1. m is an integer of 1 or greater, for example, an integer of 1 to 3, for example, 1 or 2, for example, 1. n and m may be the same or different, for example, they are the same. In some embodiments, n and m are 1, or n and m are 2, for example, n and m are 1.

[0063] SP 1 and SP 2 may be the same or different, e.g., they are symmetrical to each other. In some embodiments, SP 1 is expressed by equation (2). For example, SP 1 is expressed by equation (2), and SP 2 is expressed by one of the formulas (3) to (7). For example, SP 1 is expressed by equation (2), and SP 2 is represented by formula (3). In some embodiments, SP 1 is expressed by equation (4). For example, SP 1 is expressed by equation (4), and SP 2 is expressed by one of the formulas (4) to (7). For example, SP 1 and SP 2are independently represented by formula (4). In some embodiments, SP 1 is expressed by equation (5). For example, SP 1 is expressed by equation (5), and SP 2 is expressed by one of the formulas (4) to (7). For example, SP 1 and SP 2 are independently represented by formula (5). In some embodiments, SP 1 is expressed by equation (6). For example, SP 1 is expressed by equation (6), and SP 2 is expressed by one of the formulas (4) to (7). For example, SP 1 is expressed by equation (6), and SP 2 is represented by formula (7). In some embodiments, SP 1 is expressed by equation (7). For example, SP 1 is expressed by equation (7), and SP 2 is expressed by one of the formulas (4) to (7). For example, SP 1 is expressed by equation (7), and SP 2 is represented by formula (6): In the embodiment described in this paragraph, n and m are 1, for example.

[0064] Q in Equation (1) 1 and Q 2 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a halogen atom, or Q 1 and Q 2 are joined together, [ka] (In the formula, G 3 and G 4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group; and * represents the bonding site to the benzene ring of formula (1). 1and Q 2 may be the same or different, for example, the same. 3 and G 4 may be the same or different, e.g., are the same.

[0065] In some embodiments, Q 1 and Q 2 is a hydrogen atom. 1 and Q 2 is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, for example, 1 to 6 carbon atoms, for example, 7 to 12 carbon atoms. 1 and Q 2 is a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, for example, 1 to 6 carbon atoms, for example, 7 to 12 carbon atoms. Substituents in the alkyl and alkoxy groups may be, for example, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, or a halogen atom. In some embodiments, Q 1 and Q 2 is a halogen atom such as a fluorine atom.

[0066] In some embodiments, Q 1 and Q 2 are joined together, [ka] and the compounds of the present invention have the formula [ka] It has a structure represented by:

[0067] In some embodiments, Q 1 and Q 2 are hydrogen atoms or are bonded together to form [ka] Form.

[0068] G 1 and G 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted carbazolyl group, in particular a hydrogen atom or a substituted or unsubstituted aryl group, n and m are 1, SP 1 is represented by one of the formulas (2) and (4) to (7), for example, one of the formulas (4) to (7), in particular, formula (4), and SP 2 is represented by one of formulas (3) to (7), for example, one of formulas (4) to (7), in particular formula (4). In some embodiments, Q 1 and Q 2 are joined together, [ka] and the compounds of the present invention have the formula [ka] It has a structure represented by:

[0069] In some embodiments, G 3 and G 4 independently represent a substituted or unsubstituted aryl group, for example, a substituted or unsubstituted phenyl group. 3 and G 4 is a hydrogen atom.

[0070] In some embodiments, G 1 and G 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted carbazolyl group; n and m are 1; SP 1is represented by one of the formulas (2) and (4) to (7), for example, one of the formulas (4) to (7), in particular, formula (4), and SP 2 is represented by one of the formulas (3) to (7), for example, one of the formulas (4) to (7), in particular, formula (4), and G 3 and G 4 is a hydrogen atom or a substituted or unsubstituted aryl group.

[0071] In some embodiments, G 1 and G 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group; n and m are 1; SP 1 is represented by one of the formulas (2) and (4) to (7), for example, one of the formulas (4) to (7), in particular, formula (4), and SP 2 is represented by one of the formulas (3) to (7), for example, one of the formulas (4) to (7), in particular, formula (4), and G 3 and G 4 is a hydrogen atom or a substituted or unsubstituted aryl group.

[0072] In some embodiments, G 1 and G 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted carbazolyl group, n and m are 1, and SP 1 is represented by one of the formulas (2) and (4) to (7), for example, one of the formulas (4) to (7), in particular, formula (4), and SP 2 is represented by one of the formulas (3) to (7), for example, one of the formulas (4) to (7), in particular, formula (4), and G 3 and G 4 is a hydrogen atom or a substituted or unsubstituted aryl group.

[0073] The compound represented by formula (1) does not have any repeating units. In this application, the term "repeating unit" refers to a repeating moiety derived from one or more monomers that constitutes a polymer structure formed by the polymerization reaction of one or more monomers.

[0074] Specific examples of the compound represented by formula (1) are shown below: However, the compounds represented by formula (1) that can be used in the present invention are not limited to the following specific examples.

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] [ka]

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[0110] [ka]

[0111] [ka]

[0112] When it is intended to form an organic layer containing the compound represented by formula (1) as a coating by a vapor deposition method, the molecular weight of the compound represented by formula (1) is, for example, 1500 or less, for example, 1200 or less, for example, 1000 or less, for example, 800 or less. The lower limit of the molecular weight is the molecular weight of the smallest compound represented by formula (1).

[0113] The compound represented by formula (1) can be formed into a film by a coating method regardless of its molecular weight. Compounds having a relatively large molecular weight can be formed into a film by a coating method.

[0114] In the application of the present invention, a compound containing multiple structures each represented by formula (1) in the molecule can be used as a laser oscillation material.

[0115] For example, it may be considered to use a polymer obtained by previously introducing a polymerizable group into the structure represented by formula (1) and polymerizing the polymerizable group as a light-emitting material. 1 ~R 32 and G 1 ~G 4 It may be considered to prepare a monomer having a polymerizable functional group at either of the repeat units, homopolymerize it, or copolymerize it with another monomer to prepare a polymer containing the repeat unit, and use this polymer as a laser emission material. Alternatively, it may be considered to react a compound containing a structure represented by formula (1) to form a dimer or trimer, and use this dimer or trimer as a light emitting material.

[0116] Examples of polymers having a repeating unit containing the structure represented by formula (1) include polymers containing the structure represented by formula (8) or (9) below.

[0117] [ka]

[0118] In formula (8) and formula (9), Q represents a group containing a structure represented by formula (1), and L 1 and L 2 represents a linking group. The linking group has, for example, 0 to 20 carbon atoms, for example, 1 to 15 carbon atoms, for example, 2 to 10 carbon atoms. For example, the linking group is -X 11 -L 11-, where X 11 represents an oxygen atom or a sulfur atom, for example, an oxygen atom, and L 11 represents a linking group, for example, a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and for example, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted phenylene group.

[0119] In equations (8) and (9), R 101 , R 102 , R 103 , and R 104 each independently represents a substituent, for example, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen atom, for example, an unsubstituted alkyl group having 1 to 3 carbon atoms, an unsubstituted alkoxy group having 1 to 3 carbon atoms, a fluorine atom, or a chlorine atom, for example, an unsubstituted alkyl group having 1 to 3 carbon atoms, or an unsubstituted alkoxy group having 1 to 3 carbon atoms.

[0120] L 1 and L 2 is a linking group represented by R in the structure of formula (1) constituting Q 1 ~R 32 and G 1 ~G 4 Two or more linking groups may be attached to one group represented by Q to form a bridged or network structure.

[0121] Specific examples of the repeating unit structure include structures represented by the following formulas (10) to (13).

[0122] [ka]

[0123] A polymer having a repeating unit containing a structure represented by any one of formulas (10) to (13) is prepared by subjecting R1 ~R 32 and G 1 ~G 4 The synthesis can be carried out by introducing a hydroxyl group into either of the above, reacting the hydroxyl group as a linker with the following compound, introducing a polymerizable group thereto, and then polymerizing the polymerizable group.

[0124] [ka]

[0125] A polymer containing a structure represented by formula (1) in its molecule may be a polymer containing only repeating units having the structure represented by formula (1), or may further contain repeating units having another structure. The repeating units having the structure represented by formula (1) contained in the polymer may be of only one type, or may be of two or more types. Examples of repeating units not having the structure represented by formula (1) include repeating units derived from monomers used in ordinary copolymerization. Examples of repeating units include repeating units derived from monomers having an ethylenically unsaturated bond, such as ethylene and styrene.

[0126] Synthesis of compounds represented by formula (1) The compound represented by formula (1) can be synthesized by a known reaction. The reaction conditions can be appropriately determined. For details of the reaction, see Synthesis Example 1 below.

[0127] Organic Solid-State Lasers The present invention also provides an organic solid-state laser (organic semiconductor laser) comprising a compound represented by formula (1). The compound of formula (1) is useful as a material for use in the light-emitting layer (light amplification layer) of an organic solid-state laser. The light-emitting layer may comprise two or more compounds of formula (1), or may comprise only one compound of formula (1). The light-emitting layer may comprise a host material. In some embodiments, a host material that absorbs optical excitation light for the organic solid-state laser is used. In some embodiments, a host material is used that has sufficient spectral overlap between its own fluorescence spectrum and the absorption spectrum of the compound of formula (1) contained in the light-emitting layer. This allows efficient Förster-type energy transfer from the host material to the compound of formula (1). The concentration of the compound of formula (1) in the light-emitting layer is, for example, at least 0.1 wt%, for example, at least 1 wt%, for example, at least 3 wt%, and, for example, at most 50 wt%, for example, at most 30 wt%, for example, at most 10 wt%.

[0128] The organic solid-state laser of the present invention has an optical resonator structure. The optical resonator structure may be a one-dimensional resonator structure or a two-dimensional resonator structure. Examples of the latter include a circulator resonator structure and a whispering gallery type optical resonator structure. A distributed feedback (DFB) structure and a distributed Bragg reflector (DBR) structure can also be used. In the case of a DFB, a second-order DFB grating structure may be used. A mixed-order DFB grating structure may be used. That is, a mixed structure of DFB grating structures differing in the order of their resonant wavelength relative to the laser emission wavelength may be used. A specific example of such a structure is an optical resonator structure formed with a second-order Bragg scattering region. For details of the optical resonator structure, see the specific examples shown below. The organic solid-state laser may further include an external optical resonator structure as the optical resonator structure. For example, the optical resonator structure may be formed on a glass substrate. Examples of materials constituting the optical resonator structure include insulating materials such as SiO2. For example, a grating structure may be formed, and the grating depth is, for example, 75 nm or less, selected from the range of 10 nm to 75 nm. The depth may be, for example, 40 nm or more, or less than 40 nm.The light-emitting layer (light-amplifying layer) containing the compound of formula (1) may be formed directly on the optical resonator structure.

[0129] The organic solid-state laser may be encapsulated by sapphire or other materials to lower the lasing threshold and optimize heat dissipation under strong optical pumping. An intermediate layer may be formed between the sapphire lid and the light-emitting layer. For example, an amorphous fluorinated polymer such as CYTOP™ may be used in the intermediate layer.

[0130] Organic electroluminescent devices comprising compounds of Formula (1) emit light with high efficiency. In some embodiments, organic electroluminescent devices comprising compounds of Formula (1) emit light in the infrared region. Organic solid-state lasers comprising compounds of Formula (1) exhibit low lasing thresholds and high luminescence efficiencies, for example, in the infrared region. These devices are useful in a variety of fields, such as sensors for bioimaging and biometric authentication.

[0131] Other advantages and features of the present invention will be better understood on the basis of the following examples, given for illustrative purposes. [Example]

[0132] The present invention will be described in more detail with reference to the following synthesis examples and examples. The materials, processes, procedures, etc. shown below can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited to the specific examples shown below.

[0133] Absorption spectra were measured using a LAMBDA950 UV-visible spectrophotometer manufactured by PerkinElmer Japan Co., Ltd. Photoluminescence (PL) spectra were measured using a FP-8600 spectrofluorometer manufactured by JASCO Corporation. Photoluminescence quantum yields were measured using equipment provided by a PMA-50 multichannel spectrometer manufactured by Hamamatsu Photonics Co., Ltd.

[0134] synthesis (Synthesis Example 1) Synthesis of Compound 1 [ka]

[0135] 4,8-Dibromobenzo[1,2-c:4,5-c']bis([1,2,5]thiadiazole) (500 mg, 1.42 mmol), dibenzo[b,d]furan-3-ylboronic acid (900 mg, 4.26 mmol), bis(triphenylphosphine)palladium(II) dichloride (150 mg, 0.214 mmol), and potassium carbonate (1.6 g, 11.6 mmol) were added to a Schlenk tube under a nitrogen atmosphere. Degassed water (5 mL) and toluene (45 mL) were added, and the reaction mixture was stirred at 60 °C for 18 hours. The mixture was then cooled to room temperature, extracted with chloroform, and washed with water. The resulting organic layer was dried over magnesium sulfate and evaporated under vacuum. The crude product was then washed with hexane and purified by sublimation (280 °C, 10 -3 Purification by HCl (Pa) gave compound 1 as a deep blue powder (85 mg, 15%).

[0136] 1 H NMR(500MHz,CDCl3,ppm):8.52(s,2H);8.29(d,2H,J=6.5Hz);8.22(d,2H,J=8Hz); 8.07(d,2H,J=7.5Hz);7.65(d,2H,J=8Hz);7.54(t,2H,J=8Hz);7.42(t,2H,J=8Hz)

[0137] (Synthesis Example 2) Synthesis of Compound 2 [ka]

[0138] 4,7-Dibromobenzo[c][1,2,5]thiadiazole (500 mg, 1.70 mmol), dibenzo[b,d]furan-3-ylboronic acid (1.08 g, 5.10 mmol), bis(triphenylphosphine)palladium(II) dichloride (179 mg, 0.255 mmol), and potassium carbonate (1.88 g, 13.6 mmol) were added to a Schlenk tube under a nitrogen atmosphere. Degassed water (4 mL) and toluene (40 mL) were added, and the reaction mixture was stirred at 100 °C for 21 hours. The mixture was then cooled to room temperature, extracted with chloroform, and washed with water. The resulting organic layer was dried over magnesium sulfate and evaporated under vacuum. The crude product was then washed with chloroform and purified by sublimation (270 °C, 10 -2 Purification by HCl (Pa) gave compound 2 as a yellow powder (631 mg, 79%).

[0139] 1 H NMR(500MHz,CDCl3,ppm):8.28(s,2H);8.13(d,2H,J=8Hz);8.03(d,2H,J=8Hz);8.00(d, 2H,J=8Hz);7.95(s,2H);7.63(d,2H,J=8Hz);7.51(t,2H,J=7.5Hz);7.40(t,2H,J=7.5Hz)

[0140] (Synthesis Example 3) Synthesis of Compound 3 [ka]

[0141] 4,7-Dibromobenzo[c][1,2,5]thiadiazole (150 mg, 0.510 mmol), N,N-diphenyl-4-(2-(tributylstannyl)benzo[b]thiophen-6-yl)aniline (1.02 g, 1.50 mmol), and bis(triphenylphosphine)palladium(II) dichloride (56 mg, 0.080 mmol) were added to a Schlenk tube under a nitrogen atmosphere. Degassed toluene (15 mL) was added, and the reaction mixture was stirred at 100 °C for 24 h. The mixture was then cooled to room temperature, extracted with chloroform, and washed with water. The resulting organic layer was dried over magnesium sulfate and evaporated under vacuum. The crude product was then washed with chloroform to give compound 3 as a red powder (436 mg, 96%).

[0142] 1 H NMR(500MHz,CDCl3,ppm):8.60(s,2H);8.06(s,2H);7.99(s,2H);7.92(d,2H,J=8Hz);7 .63(d,2H,J=8Hz);7.58(d,2H,J=8Hz);7.29(m,8H);7.17(m,12H);7.06(t,4H,J=7.5Hz)

[0143] Example 1: Thin film of Compound 1 A quartz substrate was placed in a vacuum deposition chamber and a 160 nm host:guest coating of CBP (host) and compound 1 (guest) was deposited in a ratio of 1 wt %:0.03 wt %.

[0144] When the coating was irradiated with light at room temperature, luminescence was observed, with the peak absorption wavelength at 631 nm.

[0145] When the thin film was excited at 340 nm, a PL peak wavelength of 740 nm was obtained, and the PLQY was 45%. The thin film of the present invention exhibits a high PLQY in the near-infrared region.

[0146] (Example 2) Amplified spontaneous emission Thin films of Compound 1 prepared in Example 1 were used to evaluate their potential for organic semiconductor lasers. The thin films were photoexcited at 337 nm by a pulsed nitrogen laser NL100 (Stanford Research Systems, Inc.), and the CBP host strongly absorbed the light. The pump laser pulse width was approximately 3.5 ns and its repetition rate was 20 Hz. The pump intensity was controlled using a series of neutral density filters. The pump beam was focused into a 0.5 cm × 0.2 cm stripe. The photoluminescence (PL) spectrum from the edge of the organic layer was measured using an optical fiber connected to a charge-coupled device spectrometer.

[0147] Figure 1 shows the post-ASE threshold emission spectrum of a blend film of CBP and Compound 1 (97 wt %:3 wt %). At low excitation intensities, the PL spectrum was broad and independent of the pump intensity. At high excitation intensities, ASE occurred and spectral narrowing was observed. Above the ASE threshold, the full width at half maximum (FWHM) decreased to 27 nm for this sample. This ASE effect is due to spontaneously emitted photons being guided within the film and amplified by stimulated emission. Figure 2 shows the output light intensity (left vertical axis) and full width at half maximum (right vertical axis) emitted from the end face of the blend film as a function of excitation intensity. The abrupt change in slope efficiency is directly related to the ASE threshold. For the CBP:Compound 1 (97 wt %:3 wt %) film, the ASE threshold was approximately 3.0 μJ / cm. 2 It was determined that the ASE wavelength λ ASE The ASE threshold Eth was 2.5 μJ / cm. 2 This low ASE threshold is very promising for the realization of organic semiconductor lasers.

[0148] Example 3: Organic Light-Emitting Diode (OLED) Device A 30-nm-thick indium tin oxide anode was formed on a glass substrate. The glass substrate was washed with acetone and isopropanol under ultrasonication, followed by UV-ozone treatment. The substrate was then placed in a vacuum deposition system. As shown in Figure 3, a 5-nm-thick hole-injection layer (HATCN) was first deposited, followed by a 30-nm-thick layer of α-NPD as a hole-transport layer. BSBCz and compound 1 were then co-evaporated in a 1:0.05 weight ratio to form a 25-nm-thick light-emitting layer. Next, a 55-nm-thick layer of TPBi was deposited as an electron-transport layer, followed by a 1-nm-thick layer of lithium fluoride, followed by a 100-nm-thick layer of aluminum as a cathode. Thus, an organic EL device was fabricated.

[0149] The obtained organic EL device was subjected to a current test, and a voltage of 8.0 V and a current of 148 mA / cm were obtained. 2 At a current density of 1000 s, near-infrared emission (maximum emission wavelength: 755 nm) was obtained with an external quantum efficiency of 0.7%.

[0150] Example 4: Thin film of Compound 2 A quartz substrate was placed in a vacuum deposition chamber and a 200 nm host:guest coating of CBP (host) and Compound 2 (guest) was deposited in a ratio of 1 wt %:0.05 wt %.

[0151] When the coating was irradiated with light at room temperature, luminescence was observed, with the peak absorption wavelength at 400 nm.

[0152] When the thin film was excited at 340 nm, a PL peak wavelength of 524 nm and a FWHM of 57 nm were obtained, with a PLQY of 83%. The thin film of the present invention exhibits a high PLQY in the green region.

[0153] (Example 5) Amplified spontaneous emission Thin films of compound 2 prepared in Example 4 were used to evaluate their potential for organic semiconductor lasers. The thin films were photoexcited at 355 nm by a pulsed YAG laser (QS Lasers, model number MPL15100-DP-TH), and the CBP host strongly absorbed the light. The pump laser pulse width was approximately 3.5 ns and its repetition rate was 20 Hz. The pump intensity was controlled using a series of medium-density filters. The pump beam was focused into a 0.5 cm × 0.2 cm stripe. The photoluminescence (PL) spectrum from the edge of the organic layer was measured using an optical fiber connected to a charge-coupled device spectrometer.

[0154] Figure 4 shows the post-ASE threshold emission spectrum of a blend coating of CBP and Compound 2 (95 wt.%:5 wt.%). At low excitation intensities, the PL spectrum was broad and independent of the pump intensity. At high excitation intensities, ASE occurred and spectral narrowing was observed. Above the ASE threshold, the full width at half maximum (FWHM) decreased to 12 nm for this sample. This ASE effect is due to spontaneously emitted photons being guided within the coating and amplified by stimulated emission. Figure 5 shows the output light intensity (left vertical axis) and full width at half maximum (right vertical axis) emitted from the end face of the blend coating as a function of excitation intensity. The abrupt change in slope efficiency is directly related to the ASE threshold. For the CBP:Compound 2 (95 wt.%:5 wt.%) coating, the ASE threshold was approximately 14.2 μJ / cm. 2 It was determined that the ASE wavelength λ ASE The ASE threshold Eth was 14.2 μJ / cm. 2 This low ASE threshold is highly promising for the realization of organic semiconductor lasers.

Claims

1. The following formula (1): Formula (1) 【Chemistry 1】 (In the formula, G １ and G ２ each independently represents a hydrogen atom or a substituent, SP １ represents a linking group represented by one of the following formulas (2) and (4) to (7), and SP ２ represents a linking group represented by one of the following formulas (3) to (7): 【Chemistry 2】 (In the formula, R １ ~R ３２ each independently represents a hydrogen atom or a substituent, and X １ ~X ６ are each independently a sulfur atom, an oxygen atom, or N-T １ where T １ represents a substituted or unsubstituted alkyl group, and each ＊ represents the binding site), n is an integer of 1 or more, m is an integer of 1 or greater, Q １ and Q ２ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a halogen atom, or Q １ and Q ２ are joined together, 【Transformation 3】 (In the formula, G ３ and G ４ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group; and ＊ represents the bonding site to the benzene ring of formula (1).

2. Q １ and Q ２ are joined together, 【Chemistry 4】 and the compound has the formula 【Transformation 5】 2. The compound of claim 1 having a structure represented by:

3. Q １ and Q ２ are joined together, 【Transformation 6】 and the compound has the formula 【Transformation 7】 2. The compound of claim 1 having a structure represented by:

4. SP １ The compound according to claim 1 , represented by formula (2):

5. SP １ is represented by the above formula (2), and SP ２ The compound according to claim 1, represented by formula (3):

6. SP １ The compound according to claim 1 , represented by formula (4):

7. SP １ and SP ２ The compound according to claim 1 , represented by formula (4):

8. SP １ The compound according to claim 1, represented by formula (5):

9. SP １ and SP ２ The compound according to claim 1, represented by formula (5):

10. SP １ The compound according to claim 1, represented by formula (6):

11. SP １ is represented by the above formula (6), and SP ２ The compound according to claim 1, represented by formula (7):

12. SP １ The compound according to claim 1, represented by formula (7):

13. SP １ is represented by the above formula (7), and SP ２ The compound according to claim 1, represented by formula (6):

14. SP １ is represented by the above formula (2), and SP ２ The compound according to claim 1 , represented by formula (4):

15. SP １ is represented by the above formula (2), and SP ２ The compound according to claim 1, represented by formula (5):

16. SP １ is represented by the above formula (2), and SP ２ The compound according to claim 1, represented by formula (6):

17. SP １ is represented by the above formula (2), and SP ２ The compound according to claim 1, represented by formula (7):

18. X １ ~X ６ The compound of claim 1 , wherein is an oxygen atom.

19. X １ ~X ６ The compound of claim 1 , wherein is a sulfur atom.

20. 2. The compound of claim 1, wherein m and n are 1.

21. G １ and G ２ The compound of claim 1 , wherein is a hydrogen atom.

22. G １ and G ２ and each independently represent a substituted or unsubstituted diarylamino group.

23. G １ and G ２ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted carbazolyl group.

24. G ３ and G ４ The compound of claim 1 , wherein is a hydrogen atom.

25. G ３ and G ４ The compound of claim 1 , wherein each is independently a substituted or unsubstituted aryl group.

26. R １ and R ３２ The compound of claim 1 , wherein is a hydrogen atom.

27. The compound of claim 1 having a symmetrical structure. 【Request Item 28】 【Chemistry 8】 2. The compound of claim 1 selected from:

29. An organic solid state laser comprising the compound of claim 1.

30. An organic electroluminescent device comprising the compound of claim 1.

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