Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
  • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
  • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
  • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/649—Aromatic compounds comprising a hetero atom
  • H10K85/652—Cyanine dyes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/649—Aromatic compounds comprising a hetero atom
  • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/649—Aromatic compounds comprising a hetero atom
  • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
  • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
  • H10K50/14—Carrier transporting layers

Definitions

• the present invention relates to a compound having good light emitting properties.
• the present invention also relates to light emitting materials, delayed fluorescent materials and organic optical devices using the compounds.
• the singlet exciter generated by the inverse intersystem crossing from the excited triplet state to the excited singlet state is also based. Since fluorescence is emitted when transitioning to the singlet state, the energy of the triplet exciter, which has a high generation probability, can also indirectly contribute to fluorescence emission. Therefore, a significantly higher luminous efficiency can be expected as compared with the case of using a normal fluorescent light emitting material that does not cause intersystem crossing.
• thermoly activated delayed fluorescent substance is a compound in which the inverse intersystem crossing from the excited triplet state to the excited singlet state occurs due to the absorption of heat energy, and the singlet directly excited from the base singlet state. After the fluorescence radiation from the exciter is observed, the fluorescence radiation from the singlet exciter (delayed fluorescence radiation) generated via the intersystem crossing is observed with a delay.
• One is CN, The other one is A, The other p pieces are D independently, The remaining 3-p are hydrogen atoms or substituents (excluding CN, A and D).
• A is, Het-L A - a * a group represented by wherein Het is of at least two as ring skeleton constituting atoms a substituted or unsubstituted heteroaryl group (wherein the heteroaryl group bonded via a carbon atom containing a nitrogen atom) represents, L a represents a single bond or a substituted or unsubstituted arylene group, * represents a bonding position.
• D is a group represented by the following general formula (IIa), (IIb), (IIc) or (IId).
• RDs are independently hydrogen atoms, deuterium atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted amino groups, substituted or unsubstituted aryl groups, substituted or unsubstituted, respectively.
• R D' represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R D' is one or more R Ds. May be combined with to form a cyclic structure, L D is a single bond each independently represent a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group, * Represents the bond position. p is 2 or 3. The plurality of Ds present in the molecule may be the same as or different from each other. ] [2] The compound according to [1], wherein R 1 is A.
• L A represents a single bond or a substituted or unsubstituted arylene group. * Represents the bond position.
• Het-L A - * is a group represented by the general formula (IIIa), compounds described in [17].
• R 22 and R 24 are independently substituted or unsubstituted aryl groups, respectively.
• LD is a single bond.
• L D is a substituted or unsubstituted arylene group, [1] ⁇ The compound according to any one of [19].
• a luminescent material comprising the compound according to any one of [1] to [21].
• a delayed fluorescent material comprising the compound according to any one of [1] to [21].
• a compound represented by the following general formula (I') [R 1 ⁇ R 5 in the general formula (I ') satisfies the following condition 1 or condition 2, (Condition 1) Of R 1 to R 5 , One is CN, The other one is a halogen atom, The other p pieces are D independently, The remaining 3-p are hydrogen atoms or substituents (excluding CN, A and D). (Condition 2) Of R 1 to R 5 , One is CN, The other one is the first halogen atom, The other one is the second halogen atom, Yet the other p-1 pieces are D independently, The remaining 3-p are hydrogen atoms or substituents (excluding CN, A and D).
• A is, Het-L A - a * a group represented by wherein Het is of at least two as ring skeleton constituting atoms a substituted or unsubstituted heteroaryl group (wherein the heteroaryl group bonded via a carbon atom containing a nitrogen atom) represents, L a represents a single bond or a substituted or unsubstituted arylene group, * represents a bonding position.
• D is a group represented by the following general formula (IIa), (IIb), (IIc) or (IId).
• RDs are independently hydrogen atoms, deuterium atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted amino groups, substituted or unsubstituted aryl groups, substituted or unsubstituted, respectively.
• R D' represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R D' is one or more R Ds.
• L D is a single bond each independently represent a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group
• p is 2 or 3.
• the plurality of Ds present in the molecule may be the same as or different from each other.
• [32] The compound according to [31], which satisfies the condition 1.
• the present invention it is possible to provide a light emitting material having good light emitting characteristics. Further, according to the present invention, it is possible to provide an organic optical device having high luminous efficiency.
• the present invention provides a compound represented by the following general formula (I).
• R 1 to R 5 in the general formula (I) one is CN, the other one is A, the other p is D independently, and the remaining 3-p is D.
• R 3 is CN.
• R 3 is CN, R 1 is A, two of R 2, R 4 and R 5 are independently D, and the remaining one is a hydrogen atom.
• R 3 is CN, R 1 is A, two of R 2, R 4 and R 5 are independently D, and the remaining one is a substituted or unsubstituted aryl group (where A). Or excluding groups that can be D).
• R 3 is CN, R 1 is A, two of R 2, R 4 and R 5 are independently D, and the remaining one is a substituted or unsubstituted alkyl group.
• R 3 is CN, R 1 is A, and R 2 , R 4 and R 5 are D independently.
• R 3 is CN, R 1 is A, and R 2 is a hydrogen atom.
• R 3 is CN, R 1 is A, and R 2 is D.
• R 3 is CN, R 1 is A, and R 2 is a substituted or unsubstituted aryl group (except for groups that can be A or D).
• R 3 is CN, R 1 is A, and R 4 is D. In one embodiment, R 3 is CN, R 1 is A, and R 5 is D. In some embodiments, R 3 is CN, R 1 is A, and R 4 and R 5 are D independently. In one embodiment, R 3 is CN, R 1 is A, and R 2 and R 4 are D independently. In some embodiments, R 3 is CN, R 1 is A, and R 2 and R 5 are D independently.
• R 2 is CN. In one embodiment, R 2 is CN, R 1 is A , two of R 3 , R 4 and R 5 are independently D, and the remaining one is a hydrogen atom. In one embodiment, R 2 is CN, R 1 is A , two of R 3 , R 4 and R 5 are independently D, and the remaining one is a substituted or unsubstituted aryl group (where A). Or excluding groups that can be D). In some embodiments, R 2 is CN, R 1 is A , two of R 3 , R 4 and R 5 are independently D, and the remaining one is a substituted or unsubstituted alkyl group.
• R 2 is CN, R 1 is A, and R 3 , R 4 and R 5 are each independently D.
• R 2 is CN, R 1 is A, and R 3 is D.
• R 2 is CN, R 1 is A, and R 4 is D.
• R 2 is CN, R 1 is A, and R 3 and R 4 are D.
• R 2 is CN, R 1 is A, and R 3 and R 5 are D.
• R 2 is CN and R 3 is A.
• R 2 is CN, R 3 is A, and R 4 is a hydrogen atom.
• R 2 is CN, R 3 is A, and R 1 is a hydrogen atom.
• R 2 is CN, R 3 is A, and R 5 is a hydrogen atom. In one embodiment, R 2 is CN and R 4 is A. In a preferred embodiment, R 2 is CN, R 4 is A, and R 3 is a hydrogen atom. In one embodiment, R 2 is CN, R 4 is A, and R 1 is a hydrogen atom.
• R 1 is CN. In one embodiment, R 1 is CN and R 2 is A. In one embodiment, R 1 is CN, R 2 is A, two of R 3 , R 4 and R 5 are independently D, and the remaining one is a hydrogen atom. In a preferred embodiment, R 1 is CN, R 2 is A, and R 3 is a hydrogen atom. In one embodiment, R 1 is CN, R 2 is A, two of R 3 , R 4 and R 5 are independently D, and the remaining one is a substituted or unsubstituted aryl group (where A). Or excluding groups that can be D).
• R 1 is CN, R 2 is A, two of R 3 , R 4 and R 5 are independently D, and the remaining one is a substituted or unsubstituted alkyl group.
• R 1 is CN, R 2 is A, and R 3 , R 4 and R 5 are each independently D.
• R 1 is CN and R 3 is A.
• R 1 is CN, R 3 is A, two of R 2, R 4 and R 5 are independently D, and the remaining one is a hydrogen atom.
• R 1 is CN, R 3 is A, and R 2 is a hydrogen atom.
• R 1 is CN, R 3 is A, and R 4 is a hydrogen atom.
• R 1 is CN, R 3 is A, two of R 2, R 4 and R 5 are independently D, and the remaining one is a substituted or unsubstituted aryl group (where A). Or excluding groups that can be D).
• R 1 is CN, R 3 is A, two of R 2, R 4 and R 5 are independently D, and the remaining one is a substituted or unsubstituted alkyl group.
• R 1 is CN, R 3 is A, and R 2 , R 4 and R 5 are each independently D.
• R m is A and R m + 1 is a hydrogen atom, or R m is a hydrogen atom and R m + 1 is A.
• m is an integer of 1 to 4.
• R 1 is A and R 2 is a hydrogen atom.
• R 2 is A and R 3 is a hydrogen atom.
• R 3 is A and R 4 is a hydrogen atom.
• R 1 is a hydrogen atom and R 2 is A.
• R 2 is a hydrogen atom and R 3 is A.
• R 4 and R 5 are D independently of each other. In some embodiments, R 3 and R 5 are D independently of each other. In some embodiments, R 2 and R 5 are D independently. In some embodiments, R 3 , R 4 and R 5 are each independently D. In some embodiments, R 2 , R 4 and R 5 are each independently D. In some embodiments, R 2 , R 3 and R 5 are each independently D.
• R 1 to R 5 are not substituted or unsubstituted aryl groups (except for groups that can be A or D). In certain embodiments, R 1 to R 5 are not substituted or unsubstituted aryl groups (including groups that can be A or D). In certain embodiments, only one of R 1 through R 5 is a substituted or unsubstituted aryl group (except for groups that can be A or D). In certain embodiments, only one of R 1 to R 5 is a substituted or unsubstituted aryl group (including a group that can be A or D). In certain embodiments , two of R 1 to R 5 are substituted or unsubstituted aryl groups (including groups that can be A or D).
• R 1 to R 5 is CN, one is A, and the other three are not carbon atom-bonded groups.
• R 1 through R 5 are groups composed of two or more atoms, each independently selected from the group consisting of hydrogen, carbon and nitrogen atoms. In certain embodiments, R 1 through R 5 are not groups with repeating units.
• R 1 to R 5 are (A, H, CN, D, D), (D, CN, A, H). , D) and (D, CN, H, A, D).
• R 1 , R 2 , R 3 , R 4 , R 5 are (A, H, CN, D, D), (D, CN, A, H). , D) and (D, CN, H, A, D).
• (A, H, CN, D, D), (A, D, CN, H, D), (A, D, CN, D, H), (A, Ar, CN, D, D), (A, D, CN, Ar, D), (A, D, CN, D, Ar) and (A, D, CN, D, D) groups can be mentioned.
• (A, H, CN, D, D), (A, D, CN, H, D), (A, D, CN, D, H) and (A, D, CN, D, The group of D) can be mentioned. Further, as another group, the groups of (A, H, CN, D, D), (A, D, CN, H, D) and (A, D, CN, D, H) can be mentioned.
• (A, H, CN, D, D), (A, D, CN, H, D), (A, D, CN, D, H), (A, Ar, CN, D, D), (A, D, CN, Ar, D), (A, D, CN, D, Ar) and (A, D, CN, D, D) groups can be mentioned.
• (A, H, CN, D, D), (A, D, CN, H, D), (A, D, CN, D, H) and (A, D, CN, D, The group of D) can be mentioned.
• H represents a hydrogen atom
• Ar represents a substituted or unsubstituted aryl group (excluding a group that can be A or D).
• R 1 to R 5 that does not belong to the group exemplified here can also be adopted.
• Het-L A - is a group represented by *.
• Het is a substituted or unsubstituted heteroaryl group bonded via a carbon atom, and the heteroaryl group referred to here contains at least two nitrogen atoms as ring skeleton constituent atoms.
• L A represents a single bond or a substituted or unsubstituted arylene group. * Represents the bond position.
• Het has a heteroaryl ring containing two or more nitrogen atoms as ring skeleton-constituting atom, it is preferably ring skeleton-constituting carbon atoms of the heteroaryl ring is one which binds to the L A (L A Is a single bond, it is bonded to the carbon atom constituting the ring skeleton of the benzene ring of the general formula (1)).
• Het-L A - * the following general formula (IIIa) is preferably a group represented by any one of (IIIb) and (IIIc).
• R 21 to R 24 each independently represent a hydrogen atom or a substituent.
• L A represents a single bond or a substituted or unsubstituted arylene group. * Represents the bond position.
• R 21 -R 24 are each independently a hydrogen atom, a deuterium atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. Is.
• the alkyl group referred to here may be substituted with, for example, one or more substituents selected from a deuterium atom, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group.
• the aryl group and heteroaryl group referred to herein are independently selected from, for example, a heavy hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group1 It may be substituted with one or more substituents. Two or more of these substituents may be bonded to form a cyclic structure.
• R 21 and R 22 , R 22 and R 23 , and R 23 and R 24 may be combined with each other to form an annular structure.
• the cyclic structure referred to here may be a substituted or unsubstituted aromatic ring, or may be a substituted or unsubstituted aliphatic ring. Further, it may be a carbocycle or a heterocycle.
• R 21 to R 24 are independently substituted or unsubstituted alkyl groups or substituted or unsubstituted aryl groups, respectively.
• R 21 -R 24 are independently substituted or unsubstituted aryl groups, respectively.
• At least one of R 21 to R 24 is an aryl group that may be substituted with an aryl group.
• R 21 to R 24 may be the same or different, but can be the same, for example.
• one of R 21 and R 22 , R 22 and R 23 , and R 23 and R 24 bond with each other to form a benzene ring.
• one of R 21 and R 22 , R 22 and R 23 , R 23 and R 24 binds to each other to form a benzofuran ring or a benzothiophene ring.
• Het-L A - * is a group represented by the general formula (IIIa). Further, Het-L A - * can also be a group represented by any one of formulas (IIIb) or (IIIc).
• L A is a single bond. Further, in another embodiment of the present invention, L A is a substituted or unsubstituted arylene group. L A may be a 2 or 3 substituted or unsubstituted linking group which arylene groups are linked. Further, L A is only may be made of a single substituted or unsubstituted arylene group. In certain embodiments, L A is an unsubstituted arylene group. Further, in some embodiments, L A is a substituted arylene group.
• the arylene group is then substituted with one or more substituents selected from, for example, a dehydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. Two or more of these substituents may be combined to form a cyclic structure.
• the cyclic structure referred to here may be a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted aliphatic ring. Further, it may be a carbocycle or a heterocycle.
• R 21 and L A is not able to form a cyclic structure bonded to each other.
• L A is a single bond, an unsubstituted phenylene group or at least one of a phenylene group substituted by an alkyl group.
• phenylene group examples include 1,4-phenylene group, 1,3-phenylene group and 1,2-phenylene group, and 1,4-phenylene group and 1,3-phenylene group are preferable.
• A is selected from the group consisting of A1 to A12 shown below. * Represents the bond position.
• D in the general formula (I) is a group represented by the following general formulas (IIa), (IIb), (IIc) or (IId). In certain embodiments, D is a group represented by the general formula (IIa), (IIb) or (IId). In certain embodiments, D is a group represented by the general formula (IIa). In certain embodiments, D is a group represented by the general formula (IIb). In certain embodiments, D is a group represented by the general formula (IId).
• RDs are independently hydrogen atoms, deuterium atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted amino groups, substituted or unsubstituted aryl groups, substituted or unsubstituted, respectively.
• the RD is independently selected from the group consisting of a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkoxy group. In one embodiment of the invention, the RD is independently selected from the group consisting of a hydrogen atom, a deuterium atom, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aryloxy group.
• the RD is independently selected from the group consisting of a hydrogen atom, a deuterium atom, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heteroaryloxy group.
• R D are each independently a hydrogen atom or a deuterium atom.
• the number of substituents that are neither hydrogen atoms nor deuterium atoms is 3 or 4 in some embodiments, 2 in other embodiments of the invention, and 1 in some embodiments. Is.
• X' represents N- RD ', an oxygen atom or a sulfur atom. In some embodiments, X'is N- RD '. In some embodiments, X'is an oxygen atom. In some embodiments, X'is a sulfur atom.
• R D' represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R D' is one or more R Ds. May be combined with to form a cyclic structure. In certain embodiments of the present invention, R D 'are each independently a hydrogen atom or a deuterium atom.
• R D ' is a substituted or unsubstituted alkyl group. In certain embodiments of the present invention, R D 'is a substituted or unsubstituted aryl group.
• R D and L D, R D 'and L D are not able to form a cyclic structure bonded to each other.
• L D each independently represent a single bond, a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group.
• L D is a single bond.
• L D is a substituted or unsubstituted arylene group.
• L D is 2 or 3 is selected from the group consisting of substituted or unsubstituted arylene group and a substituted or unsubstituted heteroarylene group may be a linking group linked to each other.
• L D is a 2 or 3 substituted or unsubstituted linking group which arylene groups are linked.
• L D is only made of one substituted or unsubstituted arylene group.
• L D is an unsubstituted arylene group. Further, in some embodiments, L D is a substituted arylene group. The arylene group is then substituted with one or more substituents selected from, for example, a dehydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. Two or more of these substituents may be combined to form a cyclic structure.
• the cyclic structure referred to here may be a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted aliphatic ring.
• L D is a single bond, an unsubstituted phenylene group or at least one of a phenylene group substituted by an alkyl group.
• the phenylene group include 1,4-phenylene group, 1,3-phenylene group and 1,2-phenylene group, and 1,4-phenylene group and 1,3-phenylene group are preferable.
• D is selected from the group consisting of D1 to D45 shown below. In certain embodiments, D is selected from the group consisting of D1 to D6. In certain embodiments, D is selected from the group consisting of D7 and D8. In certain embodiments, D is selected from the group consisting of D9-D16. In certain embodiments, D is selected from the group consisting of D17-D40. In certain embodiments, D is selected from the group consisting of D41-D45. * Represents the bond position. Ph represents an unsubstituted phenyl group.
• 3-p of R 1 to R 5 are hydrogen atoms or substituents (excluding groups that can be CN, A and D). When p is 3, there are no hydrogen atoms or substituents (except groups that can be CN, A and D). When p is 2, there is only one hydrogen atom or substituent (except for groups that can be CN, A and D). Substituents (except groups that can be CN, A and D) are dehydrogen atoms, or substituted or unsubstituted aryl groups (except groups that can be A or D), substituted or unsubstituted alkyl.
• a group, or a substituted or unsubstituted aryloxy group preferably a substituted or unsubstituted alkoxy group, a dehydrogen atom, a substituted or unsubstituted aryl group (excluding a group which can be A or D), or a group. It is more preferably a substituted or unsubstituted alkyl group, and even more preferably a substituted or unsubstituted aryl group (except for a group which can be A or D).
• a substituted or unsubstituted phenyl group, an unsubstituted phenyl group and the like can be mentioned.
• one of R 1 to R 5 is a hydrogen atom.
• one of R 1 to R 5 is a substituted or unsubstituted aryl group (except for a group that can be A or D), for example, an unsubstituted aryl group.
• the aryl group may be substituted with one or more substituents selected from, for example, a heavy hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Two or more of these substituents may be bonded to form a cyclic structure.
• the cyclic structure referred to here may be a substituted or unsubstituted aromatic ring, or may be a substituted or unsubstituted aliphatic ring. Further, it may be a carbocycle or a heterocycle.
• p is an integer of either 2 or 3.
• the plurality of Ds present in the molecule may be the same or different from each other.
• p is 3.
• p is 2.
• none of the general formula R 1 and R 2, R 2 and R 3 of (I), R 3 and R 4, R 4 and R 5, do not form a ring structure by bonding with each other.
• the molecular weight of the compound represented by the general formula (I) is, for example, 1500 or less when the organic layer containing the compound represented by the general formula (I) is intended to be formed into a film by a vapor deposition method. It is preferably 1200 or less, more preferably 1000 or less, and even more preferably 900 or less.
• the lower limit of the molecular weight is the molecular weight of the smallest compound represented by the general formula (I).
• the compound represented by the general formula (I) may be formed by a coating method regardless of the molecular weight. By using the coating method, it is possible to form a film even if the compound has a relatively large molecular weight.
• a compound containing a plurality of structures represented by the general formula (I) in the molecule may be prepared.
• Such compounds may be used, for example, as charge transport materials.
• a polymer can be obtained by allowing a polymerizable group to exist in the structure represented by the general formula (I) in advance and polymerizing the polymerizable group.
• a monomer containing a polymerizable functional group is prepared in any of R 1 to R 5 of the general formula (I), and this is polymerized alone or copolymerized with another monomer.
• a polymer having a repeating unit can be obtained.
• a dimer or a trimer can be obtained by coupling compounds having a structure represented by the general formula (I) with each other.
• the compound represented by the general formula (I) does not contain a metal atom. In certain embodiments, the compound represented by the general formula (I) is composed only of a hydrogen atom, a carbon atom and a nitrogen atom. In certain embodiments, the compound represented by the general formula (I) is composed only of atoms selected from the group consisting of hydrogen atoms, carbon atoms, nitrogen atoms and oxygen atoms. In certain embodiments, the compound represented by the general formula (I) is composed only of atoms selected from the group consisting of hydrogen atoms, carbon atoms, nitrogen atoms and sulfur atoms.
• the compound represented by the general formula (I) is composed only of atoms selected from the group consisting of hydrogen atom, carbon atom, nitrogen atom, oxygen atom, sulfur atom and silicon atom.
• the compound represented by the general formula (I) is a diarylamino group (however, the two aryl groups constituting the diarylamino group are not bonded to each other by a single bond or a linking group to form a cyclic structure). Does not include.
• the compound represented by the general formula (I) can be synthesized by combining known reactions.
• a compound of the general formula (I) in which R 1 is A, R 2 is H, R 3 is CN, R 4 and R 5 is D can be synthesized via an intermediate by the following reaction scheme. It is possible.
• halogenated terephthalonitrile is used as a starting material.
• a halogenated terephthalonitrile having a fluorine atom at a position where D is to be introduced and a bromine atom at a position where A is to be introduced is prepared.
• the above reaction is an application of a known reaction, and known reaction conditions can be appropriately selected and used.
• a synthetic example described later can be referred to.
• the compound represented by the general formula (I) can also be synthesized by combining other known synthetic reactions.
• [R 1 ⁇ R 5 in the general formula (I ') satisfies the following condition 1 or condition 2, (Condition 1) Of R 1 to R 5 , One is CN, The other one is a halogen atom, The other p pieces are D independently, The remaining 3-p are hydrogen atoms or substituents (excluding CN, A and D).
• R 1 to R 5 One is CN, The other one is the first halogen atom, The other one is the second halogen atom, Yet the other p-1 pieces are D independently, The remaining 3-p are hydrogen atoms or substituents (excluding CN, A and D).
• A is, Het-L A - a * a group represented by wherein Het is of at least two as ring skeleton constituting atoms a substituted or unsubstituted heteroaryl group (wherein the heteroaryl group bonded via a carbon atom containing a nitrogen atom) represents, L a represents a single bond or a substituted or unsubstituted arylene group, * represents a bonding position.
• D is a group represented by the following general formula (IIa), (IIb), (IIc) or (IId).
• X' represents N- RD ', an oxygen atom or a sulfur atom
• RDs are independently hydrogen atoms, deuterium atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted amino groups, substituted or unsubstituted aryl groups, substituted or unsubstituted, respectively.
• R D' represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R D' is one or more R Ds.
• L D is a single bond each independently represent a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group, * Represents the bond position.
• p is 2 or 3.
• the plurality of Ds present in the molecule may be the same as or different from each other.
• condition 1 is satisfied.
• p is 2.
• p is 3.
• the halogen atom is a bromine atom.
• condition 2 is satisfied.
• p is 2.
• one of R 1 to R 5 is a hydrogen atom.
• the halogen atom is a fluorine atom.
• the halogen atom is a bromine atom.
• the compound represented by the general formula (I) is a luminescent material. In certain embodiments, the compound represented by the general formula (I) is a compound capable of emitting delayed fluorescence. In certain embodiments, the compound represented by the general formula (I) exhibits excellent red emission. In certain embodiments, the compounds of the general formula (I) exhibit excellent durability. In certain embodiments of the present disclosure, the compound of general formula (I), when excited by thermal or electronic means, has a blue, green, yellow, orange, red region of the UV region, visible spectrum. It can emit light in the near infrared region (eg, about 420 nm to about 500 nm, about 500 nm to about 600 nm or about 600 nm to about 700 nm).
• the near infrared region eg, about 420 nm to about 500 nm, about 500 nm to about 600 nm or about 600 nm to about 700 nm.
• the compound of general formula (I), when excited by thermal or electronic means, has a red or orange region of the visible spectrum (eg, from about 620 nm to about 780 nm, about Approx. It can emit light at 650 nm).
• the compound of general formula (I), when excited by thermal or electronic means has an orange or yellow region of the visible spectrum (eg, from about 570 nm to about 620 nm, about Approx. It can emit light at 590 nm (about 570 nm).
• the compound of general formula (I), when excited by thermal or electronic means, is in the green region of the visible spectrum (eg, from about 490 nm to about 575 nm, about 510 nm). Can emit light.
• the compound of general formula (I), when excited by thermal or electronic means is in the blue region of the visible spectrum (eg, from about 400 nm to about 490 nm, about 475 nm). Can emit light.
• the compounds represented by the general formula (I) can emit light in the ultraviolet spectral region (eg, 280-400 nm) when excited by thermal or electronic means.
• the compound of general formula (I) can emit light in the infrared spectral region (eg, 780 nm to 2 ⁇ m) when excited by thermal or electronic means.
• the compound represented by the general formula (I) is a charge transport material.
• the compound represented by the general formula (I) is used for the charge transport layer.
• the compound represented by the general formula (I) has high mobility as a charge transport material and is excellent in durability.
• an organic semiconductor device such as CMOS (complementary metal oxide semiconductor) using a compound represented by the general formula (I) can be produced.
• an organic optical device such as an organic electroluminescence device or a solid-state image sensor (for example, a CMOS image sensor) can be manufactured using a compound represented by the general formula (I).
• the electronic properties of small molecule chemical libraries can be calculated using known quantum chemistry calculations by ab initio.
• TD-DFT / B3LYP / 6-31G * can be analyzed to screen molecular fragments (parts) having HOMO above a specific threshold and LUMO below a specific threshold, and the calculated triple of that part.
• the term state is greater than 2.75 eV.
• the donor portion (“D”) when there is HOMO energy of ⁇ 6.5 eV or more (for example, ionization potential), the donor portion (“D”) can be selected. Further, for example, when there is LUMO energy (for example, electron affinity) of ⁇ 0.5 eV or less, the receptor portion (“A”) can be selected.
• the bridge moiety (“B”) is, for example, a strong conjugated system that can severely limit the acceptor and donor moieties to specific conformations, resulting in overlap between the donor and acceptor moiety ⁇ -conjugated systems. To prevent.
• compound libraries are sorted using one or more of the following properties: 1. 1. Emission near a specific wavelength 2. Calculated triplet state above a specific energy level 3.
• the difference between the lowest triplet excited state of the singlet excited state and the lowest in the 77K ( ⁇ E ST) is less than about 0.5 eV, less than about 0.4 eV, less than about 0.3 eV, Less than about 0.2 eV or less than about 0.1 eV.
• E ST value some embodiments, less than about 0.09 eV, less than about 0.08 eV, less than about 0.07 eV, less than about 0.06 eV, less than about 0.05 eV, less than about 0.04 eV, less than about 0.03eV , Less than about 0.02 eV or less than about 0.01 eV.
• the compounds represented by the general formula (I) are in excess of 25%, eg, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%. , About 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95% or higher quantum yields.
• the compound represented by the general formula (I) it is combined with a compound represented by the general formula (I), the compound is dispersed, covalently bonded to the compound, coated with the compound, carried or associated with the compound 1. Used with one or more materials (eg, small molecules, polymers, metals, metal complexes, etc.) to form solid films or layers.
• a compound represented by the general formula (I) can be combined with an electroactive material to form a film.
• the compound represented by the general formula (I) may be combined with the hole transport polymer.
• the compound represented by the general formula (I) may be combined with the electron transport polymer.
• the compound represented by the general formula (I) may be combined with the hole transport polymer and the electron transport polymer. In some cases, the compound represented by the general formula (I) may be combined with a copolymer having both a hole transport part and an electron transport part. According to the above embodiment, the electrons and / or holes formed in the solid film or layer can interact with the compound represented by the general formula (I).
• the film containing the compound of the invention represented by the general formula (I) can be formed in a wet process.
• a solution in which the composition containing the compound of the present invention is dissolved is applied to the surface, and a film is formed after removing the solvent.
• the wet process include, but are not limited to, a spin coating method, a slit coating method, an inkjet method (spray method), a gravure printing method, an offset printing method, and a flexographic printing method.
• an appropriate organic solvent capable of dissolving the composition containing the compound of the present invention is selected and used.
• a substituent eg, an alkyl group
• films containing the compounds of the invention can be formed in a dry process.
• the vacuum deposition method can be employed as the dry process, without limitation. When the vacuum vapor deposition method is adopted, the compounds constituting the film may be co-deposited from individual vapor deposition sources, or may be co-deposited from a single vapor deposition source in which the compounds are mixed.
• a mixed powder in which a powder of the compound is mixed may be used, a compression molded product obtained by compressing the mixed powder may be used, or each compound is heated and melted and cooled.
• a mixture may be used.
• the composition ratio of the plurality of compounds contained in the vapor deposition source is obtained by performing co-evaporation under the condition that the vapor deposition rates (weight loss rates) of the plurality of compounds contained in a single vapor deposition source are the same or almost the same.
• a film having a composition ratio corresponding to the above can be formed.
• a film having a desired composition ratio can be easily formed.
• a temperature at which each compound to be co-deposited has the same weight loss rate can be specified, and that temperature can be adopted as the temperature at the time of co-deposition.
• the following compounds can be preferably used as host materials.
• the following compounds can be preferably used as electron blocking materials.
• the following compounds can be preferably used as hole blocking materials.
• examples of compounds preferable as materials that can be added to each organic layer of the organic electroluminescence device will be given.
• it may be added as a stabilizing material.
• Spectrophotometer (Lambda950 manufactured by Perkin Elmer), Fluorescent spectrophotometer (FluoroMax-4 manufactured by Horiba) Photonic multi-channel analyzer (PMA-12 C10027-01 manufactured by Hamamatsu Photonics), Absolute PL quantum yield measurement system (Hamamatsu Photonics) C11347), automatic current voltage brightness measurement system (ETS-170 manufactured by System Giken), life measurement system (EAS-26C manufactured by System Giken) and streak camera (model C4334 manufactured by Hamamatsu Photonics). It is a thing.
• the compounds of the examples of the present application were used for manufacturing devices and the like after being sublimated and purified.
• Pd (dpppf) Cl 2 (0.12 g, 0.17 mmol) was added to the solution, and the mixture was stirred at 100 ° C. overnight.
• the reaction mixture was cooled to room temperature, then water (15 mL), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.34 g, 5.02 mmol), and sodium carbonate (1.06 g) were added to the mixture. 10.05 mmol) was added.
• the mixture was degassed and refilled with nitrogen.
• PdCl 2 (PPh 3 ) (0.24 g, 0.33 mmol) and toluene (30 ml) were added to the mixture and stirred at 100 ° C. for 7 hours.
• Pd (dpppf) Cl 2 (0.05 g, 0.07 mmol) was added to the solution, and the mixture was stirred at 100 ° C. overnight.
• the reaction mixture was cooled to room temperature and added to the solution with water (6 mL), 2-chloro-4,6-diphenyl-1,3,5-triazine (0.73 g, 2.83 mmol), and sodium carbonate (0.43 g, 4.06 mmol) was added.
• the mixture was degassed and refilled with nitrogen.
• PdCl 2 (PPh 3 ) (0.10 g, 0.14 mmol) and toluene (12 ml) were added to the mixture and stirred at 50 ° C. for 6 hours.
• Pd (dpppf) Cl 2 (0.07 g, 0.10 mmol) was added to the solution, and the mixture was stirred at 100 ° C. overnight.
• the reaction mixture was cooled to room temperature and added to the resulting product: water (8 mL), 2-iolated-4,6-diphenyl-1,3,5-triazine (1.02 g, 2.83 mmol), and sodium carbonate. (0.60 g, 5.66 mmol) was added.
• the mixture was degassed and refilled with nitrogen.
• PdCl 2 (PPh 3 ) (0.13 g, 0.19 mmol) and toluene (16 ml) were added to the mixture and stirred at 50 ° C. for 6 hours.
• Example 1 Neat film synthesis Each compound synthesized in Examples 1 to 6 is vapor-deposited on a quartz substrate by a vacuum deposition method under a condition of a vacuum degree of 10-3 Pa or less, and has a thickness of 70 nm. A thin film was formed.
• Example 2 Doping film synthesis
• Each compound synthesized in Examples 1 to 6 and a host material are vapor-deposited on a quartz substrate by a vacuum deposition method under conditions of a vacuum degree of 10-3 Pa or less from another vapor deposition source.
• a thin film having a thickness of 100 nm was formed at a concentration of 20% by weight of each compound.
• Organic electroluminescence device The principle of the characteristics of the illustrated organic electroluminescence device is shown below.
• organic electroluminescence devices carriers are injected into the light emitting material from the anode and cathode to form an excited state in the light emitting material, thereby emitting light.
• the excitons that give rise to the excited singlet state are usually 25% of all excitons generated, and the remaining 75% give rise to the excited triplet state. Therefore, the use of phosphorescence is light emission from the excited triplet state, which enables high energy utilization.
• the excited triplet state has a long lifetime, thus causing energy inactivation through the saturation of the excited state and the interaction with excitons in the excited triplet state, whereby the quantum yield of phosphorescence is usually Often not expensive.
• Delayed fluorescent materials transition to an excited triplet state through intersystem crossing, etc., and then to an excited singlet state through reverse intersystem crossing or absorption of thermal energy due to triplet-triplet annihilation. It emits fluorescence through the mechanism of doing.
• a thermally activated type delayed fluorescent material that emits light through absorption of thermal energy is considered to be useful for organic electroluminescence devices. When delayed fluorescent materials are used in organic electroluminescence devices, excitons in the excited singlet state usually fluoresce.
• excitons in the excited triplet state fluoresce through intersystem crossing to the excited singlet state by absorbing the heat generated by the device.
• the light emitted through the inverse intersystem crossing from the excited triple-term state to the excited single-term state has the same wavelength as fluorescence because it is light emission from the excited single-term state, but normal fluorescence and phosphorescence. It has a longer lifetime (light emission lifetime), and therefore the light is observed as fluorescence delayed from normal fluorescence and phosphorescence.
• the light can be defined as delayed fluorescence.
• the ratio of compounds in the excited singlet state is usually formed at a ratio of 25% to 25% or more through thermal energy absorption after carrier injection.
• the time-resolved spectrum was obtained by excitation light of 337 nm using a streak camera, and the component having a short emission lifetime was assigned as fluorescence, whereas the component having a long emission lifetime was assigned as delayed fluorescence.
• the lifetimes of the fluorescent component ( ⁇ prompt ) and the delayed fluorescent component ( ⁇ delay ) were calculated from the decay curve.
• the luminescent properties of the compounds synthesized in Synthesis Examples 1 to 6 are superior to the luminescent properties of the comparative compounds A and B.
• the light emission characteristic referred to here means at least one of the physical characteristic value and the element characteristic.
• the compound of the present invention has excellent light emitting properties and is also useful as a delayed fluorescent material. Therefore, the light emitting material of the present invention is effectively used for an organic optical device such as an organic electroluminescence device. Therefore, the present invention has high industrial applicability.

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