CN111039850A - Fused ring compound and preparation method and application thereof - Google Patents
Fused ring compound and preparation method and application thereof Download PDFInfo
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- CN111039850A CN111039850A CN202010038154.5A CN202010038154A CN111039850A CN 111039850 A CN111039850 A CN 111039850A CN 202010038154 A CN202010038154 A CN 202010038154A CN 111039850 A CN111039850 A CN 111039850A
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Abstract
The invention discloses a fused ring compound and a preparation method and application thereof. The fused ring compound has a structure shown as a formula (I) or a formula (II). The main body part of the compound is used as a large electron donor center and forms good pairing with an electron-withdrawing group, so that electrons and holes are transmitted in a balanced manner, and the effective combination of the electrons and the holes is promoted; the transport ability of the carrier is moderate, which avoids the minactization caused by the over-high carrier concentration; the HOMO and LUMO energy levels are matched with adjacent materials, the driving voltage is small, and the service life is obviously prolonged; the material has better thermal stability, takes proper sublimation temperature into consideration, can avoid the material from being heated and decomposed in the process of film formation or use, avoids the loss of the function of the material layer, and improves the luminous efficiency and the luminous performance of the device. The invention also provides a preparation method of the fused ring compound, an organic electroluminescent device and application of the organic electroluminescent device in a lighting device or a display device.
Description
Technical Field
The invention relates to the technical field of display, in particular to a fused ring compound and a preparation method and application thereof.
Background
In 1987, dane cloud doctor in the laboratory of Kodak corporation of america (Eastman Kodak) first made the first organic light-emitting diode (OLED) device by vacuum evaporation, and used transparent and conductive Indium Tin Oxide (ITO) as the anode, and evaporated diamine derivative and tris (8-hydroxyquinoline) aluminum on the anode in sequence, and used magnesium-silver alloy as the cathode material, and this multilayer structure can reduce the driving voltage of the OLED device, and effectively improve the charge injection problem between the material molecules and the electrode interface, and the device performance and lifetime are also improved accordingly.
Compared with an inorganic electroluminescent device (ELD), the OLED device has many advantages of low driving voltage, high luminous efficiency, high contrast, high color saturation, wide viewing angle, fast response time, and the like. In the prior art, an OLED device generally includes a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and is matched with appropriate electrodes, and each of the layers is respectively composed of the following materials: hole injection materials, hole transport materials, light emitting materials, hole blocking materials, electron transport materials, electron injection materials. The OLED light-emitting layer manufactured by adopting a doping mode has advantages in the light-emitting efficiency of the device, so that the light-emitting layer material is usually formed by doping a host material with a guest material, and the host material is an important factor influencing the light-emitting efficiency and the performance of the OLED device. 4,4' -Bis (9H-carbazol-9-yl) biphenyl (CBP) is a widely used host material for a light-emitting layer, and has good hole transport properties, but when CBP is used as a host material, the glass transition temperature of CBP is low, and thus, the CBP is easily recrystallized, which results in the decrease of the service performance and the light-emitting efficiency of an OLED device.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to overcome the defects of low stability of the host material of the light emitting layer, low energy transfer efficiency, low light emitting efficiency of the device, and short service life in the prior art, so as to provide a condensed ring compound, and a preparation method and an application thereof.
In a first aspect, the present invention provides a fused ring compound having a structure represented by formula (I) or formula (II):
R1-R14independently of one another, from hydrogen, deuterium, halogen, cyano, hydroxyl, nitro, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C60Alkyl, substituted or unsubstituted C2-C60Alkenyl of (a), substituted or unsubstituted C2-C60Alkynyl, substituted or unsubstituted C1-C60Alkylamino group of (A), substituted or unsubstituted C2-C60Substituted or unsubstituted C2-C60Alkynylamino, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C2-C60Alkenyloxy of (a), substituted or unsubstituted C2-C60Alkynyloxy of, substituted or unsubstituted C1-C60Thioalkoxy, substituted or unsubstituted C2-C60Thioalkenyloxy, substituted or unsubstituted C2-C60With a thioalkynyloxy group, substituted or unsubstituted C1-C60With an alkyl boron group, substituted or unsubstituted C2-C60With an alkene boron group, substituted or unsubstituted C2-C60With a boron alkynyl group, substituted or unsubstituted C1-C60Ester group of (1), substituted or unsubstituted C1-C60Amide group of (A), substituted or unsubstituted C4-C60Aryl, substituted or unsubstituted C3-C60Heteroaryl, substituted or unsubstituted C4-C60Aryloxy group of (1), substituted or unsubstituted C4-C60With an aromatic amine group, substituted or unsubstituted C4-C60Thioaryloxy, substituted or unsubstituted C4-C60An arylboron group of, or
R1-R14Any two to four adjacent groups are connected to form one or more groupsThe shape of the ring A is shown,
the ring A is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C60Aryl or substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring;
Ar1selected from substituted or unsubstituted groups P selected from:
C4-C60aryl of (C)3-C60Heteroaryl of (A), C4-C60Aryloxy group of (A), C4-C60Aromatic amine group of (2), C4-C60Thioaryloxy of (C)4-C60Aryl boron group of (A), C4-C60Aryl phosphine group of (A), C4-C60Heteroaryloxy of (A), C4-C60Heteroaromatic amino group of (1), C4-C60Thio-heteroaryloxy of (A), C4-C60Heteroaryl boron group of (A), C4-C60The heteroaromatic phosphine group of (1).
Further, in the condensed ring compound,
R1-R14independently of one another, from hydrogen, deuterium, halogen, cyano, hydroxy, nitro, amino, amidino, hydrazine, hydrazone, R23Substituted or unsubstituted C1-C60Alkyl of R23Substituted or unsubstituted C2-C60Alkenyl of R23Substituted or unsubstituted C2-C60Alkynyl of (A), R23Substituted or unsubstituted C1-C60Alkylamino group of (A), R23Substituted or unsubstituted C2-C60Of alkenylamino group, R23Substituted or unsubstituted C2-C60Alkynylamino of (a)23Substituted or unsubstituted C1-C60Alkoxy radical of (2), R23Substituted or unsubstituted C2-C60Alkenyloxy of (A), R23Substituted or unsubstituted C2-C60Alkynyloxy of (a), R23Substituted or unsubstituted C1-C60Thioalkoxy of、R23Substituted or unsubstituted C2-C60Thioalkenyloxy of (A), R23Substituted or unsubstituted C2-C60With a thioalkynyloxy group of23Substituted or unsubstituted C1-C60Of an alkyl group, R23Substituted or unsubstituted C2-C60Of an alkene boron group, R23Substituted or unsubstituted C2-C60With boron alkynyl, R23Substituted or unsubstituted C1-C60Ester group of (A), R23Substituted or unsubstituted C1-C60Amide group of (A), R23Substituted or unsubstituted C4-C60Aryl of (2), R23Substituted or unsubstituted C3-C60Heteroaryl of (A), R23Substituted or unsubstituted C4-C60Aryloxy group of R23Substituted or unsubstituted C4-C60Aromatic amine group of (2), R23Substituted or unsubstituted C4-C60Thioaryloxy of (A), R23Substituted or unsubstituted C4-C60An arylboron group of, or
R1-R14Any two to four adjacent groups of which are linked to form one or more groups of rings A,
the ring A is selected from R23Substituted or unsubstituted 3-7 membered carbocyclic ring, R23Substituted or unsubstituted 3-7 membered heterocyclic ring, R23Substituted or unsubstituted C4-C60Aryl or R of23Substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring;
Ar1selected from the group consisting of23A substituted or unsubstituted group P selected from:
C4-C60aryl of (C)3-C60Heteroaryl of (A), C4-C60Aryloxy group of (A), C4-C60Aromatic amine group of (2), C4-C60Thioaryloxy of (C)4-C60Aryl boron group of (A), C4-C60OfPhosphine group, C4-C60Heteroaryloxy of (A), C4-C60Heteroaromatic amino group of (1), C4-C60Thio-heteroaryloxy of (A), C4-C60Heteroaryl boron group of (A), C4-C60The hetero-aromatic phosphine group of (a),
R23independently of one another, from deuterium, halogen, nitro, cyano, R24Substituted or unsubstituted C1-C4Alkyl of R24Substituted or unsubstituted C1-C4Alkoxy radical of (2), R24Substituted or unsubstituted C1-C4Alkenyl of R24Substituted or unsubstituted C6-C12Aryl of (2), R24Substituted or unsubstituted C6-C12Aryloxy group of R24Substituted or unsubstituted C6-C12Of an arylamine group, R24Substituted or unsubstituted C3-C12Heteroaryl of (A), R24Substituted or unsubstituted C3-C12Preferably, R is23Independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, C1-C4Alkyl, halogen substituted C1-C4Alkyl, deuterium substituted C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkenyl of (a), halogen-substituted C1-C4Alkenyl, deuterium substituted C1-C4Alkenyl of, C6-C12Aryl of (C)6-C12Aryloxy group of (A), C6-C12Arylamino, halogen-substituted C6-C12Aryl, deuterium substituted C of6-C12Aryl of (C)3-C12Heteroaryl of (A), C3-C12A heteroaryl amine of (a), halogen-substituted C3-C12Heteroaryl, deuterium substituted C of3-C12The heteroaryl group of (a) is a group,
R24selected from deuterium, halogen, cyano, nitro.
Further, in the condensed ring compound,
R1-R14independently of one another, from deuterium, halogen, nitro, cyano, R23Substituted or unsubstituted groups as follows: c1-C4Alkyl of (C)2-C4Alkenyl of, C2-C4Alkynyl of (A), C1-C4Alkylamino group of (2), C2-C4Enamine group of (A), C2-C4Alkynylamino of (a), C1-C4Alkoxy group of (C)2-C4Alkenyloxy of (C)2-C4Alkynyloxy of (a), C1-C4Thioalkoxy of, C2-C4Thioalkenyloxy of (A), C2-C4Thioalkynyloxy of (C)1-C4Alkyl boron group of, C2-C4Of an alkenyl boron group, C2-C4Alkynyl boron group of C1-C4Ester group of (1), C1-C4Amide group of (1), C6-C20Aryl of (C)3-C20Heteroaryl of (A), C6-C20Aryloxy group of (A), C6-C20Aromatic amine group of (2), C6-C20Thioaryloxy of (C)6-C20The aromatic boron group of (a) is,
preferably, R1-R14Independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, C1-C4Alkyl, halogen substituted C1-C4Alkyl, deuterium substituted C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkenyl of (a), halogen-substituted C1-C4Alkenyl, deuterium substituted C1-C4Alkenyl of, C6-C12Aryl of (C)6-C12Aryloxy group of (A), C6-C12Arylamino, halogen-substituted C6-C12Aryl, deuterium substituted C of6-C12Aryl of (C)2-C12Heteroaryl of (A), C2-C12A heteroaryl amine of (a), halogen-substituted C2-C12Heteroaryl, deuterium substituted C of2-C12Or a heteroaryl group of
R1-R14Any two to four adjacent groups of which are linked to form one or more groups of rings A,
the ring A is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C12Aryl or substituted or unsubstituted C3-C12Said carbocycle is a saturated or unsaturated ring and said heterocycle is a saturated or unsaturated ring, preferably said ring A is selected from R23Substituted or unsubstituted 3-7 membered carbocyclic ring, R23Substituted or unsubstituted 3-7 membered heterocyclic ring, R23Substituted or unsubstituted C6-C12Aryl or R of23Substituted or unsubstituted C3-C12The carbocycle is a saturated or unsaturated ring, the heterocycle is a saturated or unsaturated ring,
preferably, R1-R14Independently of one another, from the group consisting of hydrogen, deuterium, halogen, methyl, ethyl, propyl, n-butyl, tert-butyl, trifluoromethyl, cyano, phenyl, biphenyl, terphenyl, pentalenyl, indenyl, naphthyl, azulenyl, heptalenyl, adamantyl, bornyl, triphenylene, indacenyl, acenaphthenyl, fluorenyl, spirobifluorenyl, benzofluorenyl, dibenzofluorenyl, phenalenyl, phenanthrenyl, anthracenyl, fluoranthryl, benzophenanthrenyl, pyrenyl, chrysenyl, tetracenyl, picenyl, perylenyl, pentylphenyl, pentacenyl, rubinyl, coronenyl, ovaphenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, thienyl, furyl, quinolyl, carbazolyl, pyranyl, thiopyranyl, phthalazinyl, phenazinyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, indolyl, indolocarbazolyl, phenanthridinyl, acridinyl, terphenyl, phenanthridinyl, phenanthrenyl, perimidine, pteridinyl, quinazolinyl, quinoxalinyl, cinnolinyl, phenanthroline, carbolinyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, dinaphthofuranyl, benzocarbazolyl, dibenzocarbazolyl, dibenzothiapyrrolyl, benzonaphthothiapyrrolyl, dinaphthothiazolyl, benzimidazolyl, imidazopyridinyl;
preferably, ring a is selected from phenyl, biphenyl, terphenyl, pentalenyl, indenyl, naphthyl, azulenyl, heptalenyl, adamantyl, bornyl, triphenylene, indacenyl, acenaphthenyl, fluorenyl, spirobifluorenyl, benzofluorenyl, dibenzofluorenyl, phenalenyl, phenanthrenyl, anthracenyl, fluoranthenyl, benzophenanthrenyl, pyrenyl, chrysenyl, tetracenyl, picenyl, peryleneyl, pentaphenyl, pentacenyl, rubinyl, coronenyl, egg phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, thienyl, furyl, quinolinyl, carbazolyl, pyranyl, thiapyranyl, phthalazinyl, phenazinyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, indolyl, indolocarbazolyl, phenanthridinyl, acridinyl, perimidine, pteridinyl, quinazolinyl, quinoxalinyl, cinnolinyl, phenanthrolinyl, alloline, phenanthrolinyl, Carboline group, benzofuranyl group, benzothiophenyl group, dibenzofuranyl group, dibenzothiophenyl group, benzonaphthofuranyl group, dinaphthofuranyl group, benzocarbazolyl group, dibenzocarbazolyl group, dibenzothiapyrrolyl group, benzonaphthothiapyrrolyl group, dinaphthothiapyrrolyl group, benzimidazolyl group, imidazopyridinyl group.
Further, in the condensed ring compound,
Ar1is composed of
X1-X6Independently of one another, from N or CR15The number of N is 0 to 3,
it is shown that the connecting key is,
R15independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30Arylboron group of (A), substituted or unsubstituted C4-C30Preferably, R is15Independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, R25Substituted or unsubstituted C1-C30Alkyl of R25Substituted or unsubstituted C2-C30Alkenyl of R25Substituted or unsubstituted C4-C30Aryl of (2), R25Substituted or unsubstituted C3-C30Heteroaryl of (A), R25Substituted or unsubstituted C4-C30Aryloxy group of R25Substituted or unsubstituted C4-C30Aromatic amine group of (2), R25Substituted or unsubstituted C4-C30Thioaryloxy of (A), R25Substituted or unsubstituted C4-C30Aryl boron group of R25Substituted or unsubstituted C4-C30An aryl phosphorus group of, or
Two adjacent R15Are connected to form a ring B,
the ring B is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30Said carbocycle is a saturated or unsaturated ring and said heterocycle is a saturated or unsaturated ring, preferably said ring B is selected from R25Substituted or unsubstituted 3-7 membered carbocyclic ring, R25Substituted or unsubstituted 3-7 membered heterocyclic ring, R25Substituted or unsubstituted C4-C30Aryl or R of25Substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, the heterocycle is a saturated or unsaturated ring,
preferably, Ar1Is selected from
Q1-Q3Independently of one another, from N or CR21Preferably, Q1-Q3At least one of the N groups is N,
Q4-Q5independently of one another, from the group consisting of single bonds, NR21O, S, preferably Q4Is a single bond, Q5Is O, S or NR21Or Q4Is O, S or NR21，Q5Is a single bond, and is a single bond,
Q6-Q7are independently selected from N, CR21，
n5 is an integer of 0 to 2, n6 is an integer of 0 to 4,
L1selected from single bond, R25Substituted or unsubstituted C6-C60The aryl group of (a) is,
Ar2、R20、R21independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, R25Substituted or unsubstituted C1-C4Alkyl of R25Substituted or unsubstituted C2-C4Alkenyl of R25Substituted or unsubstituted C6-C30Aryl of (2), R25Substituted or unsubstituted C3-C30Heteroaryl of (A), R25Substituted or unsubstituted C6-C30Aryloxy group of R25Substituted or unsubstituted C6-C30Aromatic amine group of (2), R25Substituted or unsubstituted C3-C30Heteroaromatic amino group of (2), R25Substituted or unsubstituted C6-C30Thioaryloxy of (A), R25Substituted or unsubstituted C6-C30Aryl boron group of R25Substituted or unsubstituted C6-C30An aryl phosphorus group of, or
R20Two R not connected or adjacent to each other20Are connected to form a ring C,
the ring C is selected from R25Substituted or unsubstituted 3-7 membered carbocyclic ring, R25Substituted or unsubstituted 3-7 membered heterocyclic ring, R25Substituted or unsubstituted C6-C30Aryl or R of25Substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, the heterocycle is a saturated or unsaturated ring,
R25independently of one another, from deuterium, halogen, nitro, cyano, R26Substituted or unsubstituted C1-C4Alkyl of R26Substituted or unsubstituted C1-C4Alkoxy radical of (2), R26Substituted or unsubstituted C1-C4Alkenyl of R26Substituted or unsubstituted C6-C12Aryl of (2), R26Substituted or unsubstituted C6-C12Aryloxy group of R26Substituted or unsubstituted C6-C12Of an arylamine group, R26Substituted or unsubstituted C3-C12Heteroaryl of (A), R26Substituted or unsubstituted C3-C12The heteroaromatic amine group of (a) is,
R26selected from deuterium, halogen, cyano, nitro; or
Ar1Is selected from
It is shown that the connecting key is,
T1-T2independently of one another, selected from the group consisting of single bonds, O, S, SO2、CO、NR17、C(R17)2、POR17，
n1 is an integer of 0 to 3, n2 is an integer of 0 to 4, n3 is an integer of 0 to 3, n4 is an integer of 0 to 4,
R16independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30Arylboron group of (A), substituted or unsubstituted C4-C30Preferably, R is16Independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, R25Substituted or unsubstituted C1-C30Alkyl of R25Substituted or unsubstituted C2-C30Alkenyl of R25Substituted or unsubstituted C4-C30Aryl of (2), R25Substituted or unsubstituted C3-C30Heteroaryl of (A), R25Substituted or unsubstituted C4-C30Aryloxy group of R25Substituted or unsubstituted C4-C30Aromatic amine group of (2), R25Substituted or unsubstituted C4-C30Thioaryloxy of (A), R25Substituted or unsubstituted C4-C30Aryl boron group of R25Substituted or unsubstituted C4-C30An aryl phosphorus group of, or
Two adjacent R16Are connected to form a ring D,
the ring D is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30Said carbocycle is a saturated or unsaturated ring and said heterocycle is a saturated or unsaturated ring, preferably said ring D is selected from R25Substituted or unsubstituted 3-7 membered carbocyclic ring, R25Substituted or unsubstituted 3-7 membered heterocyclic ring, R25Substituted or unsubstituted C4-C30Aryl or R of25Substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, the heterocycle is a saturated or unsaturated ring,
R17independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstitutedUnsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30Preferably, R is17Independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, R25Substituted or unsubstituted C1-C30Alkyl of R25Substituted or unsubstituted C2-C30Alkenyl of R25Substituted or unsubstituted C4-C30Aryl of (2), R25Substituted or unsubstituted C3-C30Heteroaryl of (A), R25Substituted or unsubstituted C4-C30Aryloxy group of R25Substituted or unsubstituted C4-C30Aromatic amine group of (2), R25Substituted or unsubstituted C4-C30Thioaryloxy of (A), R25Substituted or unsubstituted C4-C30An arylboron group of, or
Two adjacent R17Are connected to form a ring E,
the ring E is selected from a substituted or unsubstituted cyclic 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30Said carbocycle is a saturated or unsaturated ring and said heterocycle is a saturated or unsaturated ring, preferably said ring E is selected from R25Substituted or unsubstituted cyclic 3-7 membered carbocyclic ring, R25Substituted or unsubstituted 3-7 membered heterocyclic ring, R25Substituted or unsubstituted C4-C30Aryl or R of25Substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring; or
Ar1Is composed of
Y1-Y5Independently of one another from NR18、CR18O or S, NR18The number of (a) is 0 to 3,
represents a single bond, and is a hydrogen atom,
R18independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30Preferably, R is18Independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, R25Substituted or unsubstituted C1-C30Alkyl of R25Substituted or unsubstituted C2-C30Alkenyl of R25Substituted or unsubstituted C4-C30Aryl of (2), R25Substituted or unsubstituted C3-C30Heteroaryl of (A), R25Substituted or unsubstituted C4-C30Aryloxy group of R25Substituted or unsubstituted C4-C30Aromatic amine group of (2), R25Substituted or unsubstituted C4-C30Thioaryloxy of (A), R25Substituted or unsubstituted C4-C30An arylboron group of, or
Two adjacent R18Are connected to form a ring F,
the ring F is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted3-7 membered heterocyclic ring, substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30Said carbocycle is a saturated or unsaturated ring and said heterocycle is a saturated or unsaturated ring, preferably said ring F is selected from R25Substituted or unsubstituted 3-7 membered carbocyclic ring, R25Substituted or unsubstituted 3-7 membered heterocyclic ring, R25Substituted or unsubstituted C4-C30Aryl or R of25Substituted or unsubstituted C3-C30The carbocyclic ring is a saturated or unsaturated ring, and the heterocyclic ring is a saturated or unsaturated ring.
Further, in the condensed ring compound,
Ar1selected from the group consisting of19A substituted or unsubstituted group G selected from:
the substituent R19Independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, C1-C4Alkyl, halogen substituted C1-C4Alkyl, deuterium substituted C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkenyl of (a), halogen-substituted C1-C4Alkenyl, deuterium substituted C1-C4Alkenyl of, C6-C12Aryl of (C)6-C12Aryloxy group of (A), C6-C12Arylamino, halogen-substituted C6-C12Aryl, deuterium substituted C of6-C12Aryl of (C)2-C12Heteroaryl of (A), C2-C12A heteroaryl amine of (a), halogen-substituted C2-C12Heteroaryl, deuterium substituted C of2-C12The heteroaryl group of (a);
preferably, the substituent R19Independently of one another, from hydrogen, deuterium, halogen, methyl, deuterated methyl, trifluoromethyl, ethyl, propyl, tert-butyl, cyano, vinyl, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, phenanthrenyl or grate, benzofuranyl, benzothienyl, carbazolyl,
wherein the content of the first and second substances,
indicating a bond, ＊ indicating a binding site.
Further, in the condensed ring compound,
Ar1selected from the group consisting of27A substituted or unsubstituted group M selected from:
R27independently of one another, from deuterium, halogen, cyano, nitro, C1-C4Alkyl, deuterium substituted C1-C4Alkyl, halogen substituted C1-C4Alkyl of (C)1-C4Alkenyl of, C6-C20Aryl, deuterium substituted C of6-C20Aryl, cyano-substituted C6-C20Aryl, halogen substituted C6-C20Aryl, trifluoromethyl substituted C6-C20Aryl of (C)3-C12Heteroaryl, deuterium substituted C of3-C12Heteroaryl, cyano-substituted C of3-C12Heteroaryl, halogen substituted C of3-C12Heteroaryl, trifluoromethyl substituted C of3-C12The heteroaryl group of (a) is a group,
wherein the content of the first and second substances,
it is shown that the connecting key is,
l is selected from a single bond, R28Substituted or unsubstituted C6-C20The aryl group of (a) is,
T1、T2independently of one another, from O, S, C (R)28)2、NR28，
R28Independently of one another, from hydrogen, deuterium, halogen, cyano, nitro, R29Substituted or unsubstituted C1-C4Alkyl of R29Substituted or unsubstituted C6-C12The aryl group of (a) is,
R29selected from deuterium, halogen, cyano, nitro,
preferably, R28Independently of one another, from the group consisting of methyl, phenyl, deuterated methyl, deuterated phenyl, halogen-substituted methyl, halogen-substituted phenyl.
Further, in the condensed ring compound, Ar is1Are electron withdrawing groups.
Further, the condensed ring compound has a molecular structure shown in any one of the following formulas:
in a second aspect, the present invention provides a process for producing the above-mentioned fused ring compound,
the synthesis steps of the compound shown in the formula (I) are as follows:
taking a compound shown in a formula (A) and a compound shown in a formula (B) as initial raw materials, and carrying out Suzuki coupling reaction to obtain an intermediate 1-A; reacting the intermediate 1-A with a compound shown as a formula (C) to obtain an intermediate 2-A; carrying out coupling reaction on the intermediate 2-A and a compound shown as a formula (D) to obtain an intermediate 3-A; carrying out coupling and ring-closing reaction on the intermediate 3-A to obtain an intermediate 4-A; carrying out nitro reduction and ring closure reaction on the intermediate 4-A to obtain an intermediate 5-A; carrying out coupling reaction on the intermediate 5-A and a compound shown as a formula (E) to obtain a compound shown as a formula (I);
the synthetic route of the compound shown in the formula (I) is shown as follows:
(ii) a The synthesis steps of the compound shown in the formula (II) are as follows:
taking a compound shown in a formula (F) and a compound shown in a formula (G) as initial raw materials, and carrying out Suzuki coupling reaction to obtain an intermediate 1-B; reacting the intermediate 1-B with a compound shown as a formula (H) to obtain an intermediate 2-B; carrying out coupling reaction on the intermediate 2-B and a compound shown as a formula (J) to obtain an intermediate 3-B; the intermediate 3-B is subjected to coupling ring-closing reaction to obtain an intermediate 4-B; carrying out nitro reduction and ring closure reaction on the intermediate 4-B to obtain an intermediate 5-B; carrying out coupling reaction on the intermediate 5-B and a compound shown as a formula (K) to obtain a compound shown as a formula (II);
the synthetic route of the compound shown in the formula (II) is shown as follows:
wherein X is halogen, preferably X is selected from bromine or chlorine.
In a third aspect, the present invention provides an organic electroluminescent device comprising a substrate, a first electrode and a second electrode formed on the substrate, and an organic layer disposed between the first electrode and the second electrode, the organic layer containing the above-mentioned condensed ring compound,
the organic layer comprises at least one of a luminescent layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole blocking layer and an electron blocking layer,
preferably, the light-emitting layer includes a host material containing the above-described condensed ring compound and a dopant material,
furthermore, the weight portion of the main material is 90-99.99 parts, and the weight portion of the doping material is 0.01-10 parts;
preferably, the weight portion of the main material is 90-99 parts, and the weight portion of the doping material is 1-10 parts;
more preferably, the weight part of the main material is 93-98 parts, and the weight part of the doping material is 2-7 parts.
Further, the organic layer further includes a light-emitting auxiliary layer containing the above-described condensed ring compound.
In a fourth aspect, the present invention provides the use of the above-described organic electroluminescent device in a lighting apparatus or a display apparatus.
In a fifth aspect, the present invention provides a display apparatus comprising the above organic electroluminescent device.
In a sixth aspect, the present invention provides a lighting apparatus comprising the above organic electroluminescent device.
The technical scheme of the invention has the following advantages:
1. the fused ring compound provided by the invention has a structure shown in a formula (I) or a formula (II), and a main body part of the compound is used as a large electron donor center and forms good pairing with an electron-withdrawing group, so that electrons and holes are transmitted in a balanced manner, and the effective combination of the electrons and the holes is promoted; the transport ability of the carrier is moderate, which avoids the minactization caused by the over-high carrier concentration; the HOMO and LUMO energy levels are matched with adjacent materials, the driving voltage is small, and the service life is obviously prolonged.
2. The fused ring compound provided by the invention has larger molecular structure size and better intramolecular conjugation, so that the fused ring compound has better thermal stability, takes proper sublimation temperature into consideration, can avoid the material from being heated and decomposed in the film forming or using process, avoids the loss of the function of a material layer, and improves the luminous efficiency and the luminous performance of a device.
3. The fused ring compound provided by the invention has a three-dimensional structure, molecules are not easy to stack, energy transfer caused by the stacking of the molecules can be avoided, the generation of high-energy excitons is avoided, and annihilation caused by the existence of the high-energy excitons is effectively reduced.
4. The preparation method of the fused ring compound provided by the invention has the advantages of easily obtained starting materials, mild reaction conditions and simple operation steps, and provides a simple and easily-realized preparation method for large-scale production and application of the fused ring compound.
5. The organic electroluminescent device provided by the invention has the advantages that the condensed ring compound is used as an organic layer material, the condensed ring compound has excellent thermal stability, the condensed ring compound has HOMO and LUMO energy levels which can be matched with adjacent layers, the driving voltage is low, exciton annihilation caused by molecular stacking can be avoided, the prepared organic electroluminescent device has high luminous efficiency and long service life, and the organic electroluminescent device can be used for lighting devices or display devices.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph showing the theoretical calculation results of the HOMO level, LUMO level and energy band gap Eg of Compound 13 in Synthesis example 13 according to the present invention;
fig. 2 is a schematic structural view of an organic electroluminescent device in an embodiment of the device of the present invention.
Description of reference numerals:
1-substrate, 2-anode, 3-hole injection layer, 4-hole transport layer, 5-luminescent layer, 6-electron transport layer, 7-electron injection layer, 8-cathode.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "first", "second", and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims. In the drawings, the size and relative sizes of layers and regions may be exaggerated for clarity. It will be understood that when an element such as a layer is referred to as being "formed on" or "disposed on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly formed on" or "directly disposed on" another element, there are no intervening elements present.
Aryl-as used herein, is a monocyclic, polycyclic, spiro, or fused ring system, and may be selected, for example, from phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, phenylphenanthryl, anthracenyl, indenyl, triphenylene, pyrenyl, tetracenyl, perylenyl, chrysenyl, condensed tetraphenyl, fluoranthenyl, or spiro-dibenzofluorenyl, and the like.
Heteroaryl-as used herein, comprises at least one atom of N, O, S, P, Si, B, which may be one atom or a plurality of different atoms; the ring may be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, or the like; the ring may be monocyclic, polycyclic, spiro, fused ring, or the like, and may be selected from, for example, furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, or dihydroacridinyl.
Examples of the Compounds
(1) Compounds 1-38:
(2) compound II-i-C-1 to compound II-i-C-80:
(3) compound I-C-1 to compound I-C-80:
in the general formula I, R6Respectively identical with R in compound II-I-C-1 to compound II-I-C-801，R5Respectively identical with R in compound II-I-C-1 to compound II-I-C-802，R4Respectively identical with R in compound II-I-C-1 to compound II-I-C-803，R14Respectively identical with R in compound II-I-C-1 to compound II-I-C-807，R13Respectively identical with R in compound II-I-C-1 to compound II-I-C-808，R12Respectively identical with R in compound II-I-C-1 to compound II-I-C-809，R9Respectively identical with R in compound II-I-C-1 to compound II-I-C-8010，R8Respectively identical with R in compound II-I-C-1 to compound II-I-C-8011，R7Respectively identical with R in compound II-I-C-1 to compound II-I-C-8012，R3Respectively identical with R in compound II-I-C-1 to compound II-I-C-8013，R2Respectively identical with R in compound II-I-C-1 to compound II-I-C-805，R1Respectively identical with R in compound II-I-C-1 to compound II-I-C-806，Ar1Respectively identical with Ar in compound II-I-C-1 to compound II-I-C-801。
(4) Compound II-i-D-1 to compound II-i-D-70:
(5) compound I-D-1 to compound I-D-70:
in the general formula I, R6Respectively identical with R in compound II-I-D-1 to compound II-I-D-701，R5Respectively identical with R in compound II-I-C-1 to compound II-I-C-702，R4Respectively identical with R in compound II-I-C-1 to compound II-I-C-703，R14Respectively identical with R in compound II-I-D-1 to compound II-I-D-707，R13Respectively identical with R in compound II-I-D-1 to compound II-I-D-708，R12Respectively identical with R in compound II-I-D-1 to compound II-I-D-709，R9Respectively identical with R in compound II-I-D-1 to compound II-I-D-7010，R8Respectively identical with R in compound II-I-D-1 to compound II-I-D-7011，R7Respectively identical with R in compound II-I-D-1 to compound II-I-D-7012，R3Respectively identical with R in compound II-I-D-1 to compound II-I-D-7013，R2Respectively identical with R in compound II-I-D-1 to compound II-I-D-705，R1Respectively identical with R in compound II-I-D-1 to compound II-I-D-706，Ar1Respectively identical with Ar in compound II-I-D-1 to compound II-I-D-701。
(6) Compound II-i-E-1 to compound II-i-E-75:
(7) compound I-E-1 to compound I-E-75:
in the general formula I, R6Respectively identical with R in compound II-I-E-1 to compound II-I-E-751，R5Respectively identical with R in compound II-I-C-1 to compound II-I-C-752，R4Respectively identical with R in compound II-I-C-1 to compound II-I-C-753，R14Respectively identical with R in compound II-I-E-1 to compound II-I-E-757，R13Respectively identical with R in compound II-I-E-1 to compound II-I-E-758，R12Respectively identical with R in compound II-I-E-1 to compound II-I-E-759，R9Respectively identical with R in compound II-I-E-1 to compound II-I-E-7510，R8Respectively identical with R in compound II-I-E-1 to compound II-I-E-7511，R7Respectively identical with R in compound II-I-E-1 to compound II-I-E-7512，R3Respectively identical with R in compound II-I-E-1 to compound II-I-E-7513，R2Respectively identical with R in compound II-I-E-1 to compound II-I-E-755，R1Are respectively the same asR in compound II-I-E-1 to compound II-I-E-756，Ar1Respectively identical with Ar in compound II-I-E-1 to compound II-I-E-751。
(8) Compound II-i-F-1 to compound II-i-F-66:
(9) compound II-I-F-67 to compound II-I-F-133:
in the general formula II, Q6Is CH, Q7Is N, and the rest groups are respectively the same as compound II-I-F-1 to compound II-I-F-66.
(10) Compound II-i-F-134 to compound II-i-F-200:
in the general formula II, Q6Is N, Q7Is CH, and the rest groups are respectively the same as compound II-I-F-1 to compound II-I-F-66.
(11) Compound i-F-1 to compound i-F-200:
in the general formula I, R6Respectively identical with R in compound II-I-F-1 to compound II-I-F-2001，R5Respectively identical with R in compound II-I-C-1 to compound II-I-C-2002，R4Respectively identical with R in compound II-I-C-1 to compound II-I-C-2003，R14Respectively identical with R in compound II-I-F-1 to compound II-I-F-2007，R13Respectively identical with R in compound II-I-F-1 to compound II-I-F-2008，R12Respectively identical with R in compound II-I-F-1 to compound II-I-F-2009，R9Respectively identical with R in compound II-I-F-1 to compound II-I-F-20010，R8Respectively identical with R in compound II-I-F-1 to compound II-I-F-20011，R7Respectively identical with R in compound II-I-F-1 to compound II-I-F-20012，R3Respectively identical with R in compound II-I-F-1 to compound II-I-F-20013，R2Respectively identical with R in compound II-I-F-1 to compound II-I-F-2005，R1Respectively identical with R in compound II-I-F-1 to compound II-I-F-2006，Ar1Respectively identical with Ar in compound II-I-F-1 to compound II-I-F-2001。
Synthetic examples
Synthesis example 1
The synthetic route for compound 1 is shown below:
wherein the synthetic route of the intermediate 5-E is shown as follows:
the preparation method of the compound 1 specifically comprises the following steps:
(1) synthesis of intermediates 1-E:
taking a 500 ml double-neck round-bottom flask, putting a stirrer and an upper connecting reflux pipe into the flask, drying the flask, and filling nitrogen into the flask; the compounds o-nitrobenzoic acid (16.70 g, 1 equivalent, 0.1mol), o-bromoiodobenzene (28.19 g, 1.0 equivalent, 0.1mol), potassium carbonate (K) were added separately2CO31.5 equivalents), ethanol (50 ml), water (50 ml), toluene (200 ml), tetrakis (triphenylphosphine) palladium (Pd (PPh)3)40.05 eq), then heated to reflux and reacted for 12 hours, and cooled to room temperature after the reaction is completed; quenched by addition of 200 ml of water, dichloromethane (3X 400 ml)Liter) extracting; adding magnesium sulfate into the obtained extract liquid in sequence, drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/hexane, 1/10) to afford intermediates 1-E (17.45 g, 63% yield).
(2) Synthesis of intermediates 2-E:
taking a 500 ml double-neck round-bottom flask, putting a stirrer and an upper connecting reflux pipe into the flask, drying the flask, and filling nitrogen into the flask; intermediates 1-E (27.70 g, 1 eq, 0.1mol), bis-pinacolato diboron (25.41 g, 1 eq), potassium acetate (potassium acetate, 19.61 g, 2 eq), (1, 1' -bis (diphenylphosphino) ferrocene) dichloropalladium (II) (Pd (dppf) Cl) were added separately20.025 eq), 1, 4-dioxane (200 ml), at 120 ℃ for 8 hours; after completion of the reaction, it was cooled to room temperature, quenched with water, extracted with dichloromethane (200 ml. times.3), the extract was dried over anhydrous magnesium sulfate, spun-dried, and the crude product was isolated by silica gel column chromatography to give intermediate 2-E (19.84 g, 61% yield).
(3) Synthesis of intermediate 3-E:
taking a 500 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and adding the intermediate 2-E (1 equivalent, 0.1mol), 1, 8-dibromonaphthalene (28.59 g, 1 equivalent) and potassium carbonate (K) respectively2CO31.5 eq), ethanol (25 ml), water (25 ml), toluene (100 ml), tetrakis (triphenylphosphine) palladium (Pd (PPh)3)40.05 eq), the mixture was refluxed for 12 hours; cooling to room temperature after reaction, adding water into a reaction system, extracting by dichloromethane, sequentially adding magnesium sulfate into the obtained extract, drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/hexane, 1/10) to afford intermediate 3-E (23.37 g, 58% yield).
(4) Synthesis of intermediates 4-E:
a500 ml two-neck round-bottom flask was taken and placed with a stirrer and an upper reflux tube, dried and charged with nitrogen, and the intermediate 3-E (40.30 g, 1 equivalent, 0.1mol), dichlorobis (tricyclohexylphosphine) palladium (PdCl) were added separately2(PCy3)23.69 g, 0.05 eq), pivalic acid (t-BuCO)2H, 2 equivalents), cesium carbonate (Cs)2CO32 eq), dimethylacetamide (200 ml), stirred at 120 ℃ for 10 hours; after completion of the reaction, it was cooled to room temperature, the reaction was concentrated, and the crude product was purified by chromatography (ethyl acetate/hexane, 1/10) to afford intermediate 4-E (25.44 g, 79% yield).
(5) Synthesis of intermediate 5-E:
taking a 500 ml double-neck round-bottom bottle, placing a stirrer and an upper reflux pipe, drying, introducing nitrogen, and adding 4-E (32.31 g, 1 equivalent, 0.1mol) and triethyl phosphite (P (OEt)31 eq), 1, 2-dichlorobenzene (100 ml), followed by heating at 180 ℃ for 12 hours; after completion of the reaction, it was cooled to room temperature, the reaction was concentrated, and the crude product was purified by chromatography (ethyl acetate/hexane, 1/10) to give intermediate 5-E (20.67 g, 71% yield).
(6) Synthesis of Compound 1:
a500 ml two-necked round-bottomed flask was taken, and a stirrer and an upper reflux tube were placed in the flask, followed by drying, nitrogen gas introduction, and addition of intermediate 5-E (29.11 g, 1 equivalent, 0.1mol), compound I-1(37.50 g, 1 equivalent), cesium carbonate (3 equivalents), and tris (dibenzylideneacetone) dipalladium (Pd) respectively2(dba)30.05 equivalent), 2-dicyclohexylphosphonium-2 ', 4', 6 ' -triisopropylbiphenyl (xphos, 42.32 g, 0.05 equivalent), then toluene was added and the mixture was refluxed for 24 hours; cooling to room temperature after reaction, filtering the reaction system and concentrating; the crude product was purified by chromatography (ethyl acetate/hexane, 1/10), compound 1(41.62 g, 71% yield).
Elemental analysis: c42H26N4Theoretical value: c, 85.98; h, 4.47; n, 9.55; measured value: c, 85.95; h, 4.49; n, 9.56; HRMS (ESI) M/z (M)+): theoretical value: 586.2157, respectively; measured value: 586.2164.
synthesis example 2
The synthetic route for compound 2 is shown below:
wherein the synthetic route of the intermediate 5-E' is shown as follows:
the preparation method of the compound 2 specifically comprises the following steps:
(1) synthesis of intermediate 1-E':
the difference of the synthesis method of the intermediate 1-E is that 1-bromo-8 iodonaphthalene (1 equivalent, 0.1mol) is used for replacing o-bromoiodobenzene, the proportion of the raw materials is adjusted to obtain the intermediate 1-E' (22.56 g, 69% of yield)
(2) Synthesis of intermediate 2-E':
the difference from the synthesis of intermediate 2-E is that intermediate 1-E ' was replaced by intermediate 1-E ' (32.70 g, 1 eq, 0.1mol), and the proportions of the starting materials were adjusted to give intermediate 2-E ' (24.39 g, 65% yield).
(3) Synthesis of intermediate 3-E':
the difference from the synthesis of intermediate 3-E is that intermediate 2-E '(1 eq, 0.1mol) was used instead of intermediate 2-E, o-dibromobenzene (23.59 g, 1 eq) was used instead of 1, 8-dibromonaphthalene, and the proportions of the starting materials were adjusted to give intermediate 3-E' (22.17 g, 55% yield).
(4) Synthesis of intermediate 4-E':
the same synthesis method as intermediate 4-E was used, except that intermediate 3-E '(40.30 g, 1 eq, 0.1mol) was used instead of intermediate 3-E, and the proportions of the starting materials were adjusted to give intermediate 4-E' (16.16 g, 50% yield).
(5) Synthesis of intermediate 5-E':
the same synthesis method as intermediate 5-E was used, except that intermediate 4-E '(32.31 g, 1 equivalent, 0.1mol) was used instead of intermediate 4-E, and the proportions of the respective starting materials were adjusted to give intermediate 5-E' (21.83 g, 75% yield).
(6) Synthesis of Compound 2:
the synthesis of compound 1 was performed in a manner different from that of intermediate 5-E (29.11 g, 1 equivalent, 0.1mol) instead of intermediate 5-E, and the proportions of the respective starting materials were adjusted to obtain compound 2(41.03 g, yield 70%).
Elemental analysis：C42H26N4Theoretical value: c, 85.98; h, 4.47; n, 9.55; measured value: c, 85.95; h, 4.47; n, 9.58; HRMS (ESI) M/z (M)+): theoretical value: 586.2157, respectively; measured value: 586.2155.
synthesis example 3
The synthetic route for compound 3 is shown below:
the synthesis route of intermediate 5-E is the same as in example 1.
The preparation method of the compound 3 specifically comprises the following steps:
(1) - (5) same as in example 1;
(6) synthesis of Compound 3:
the procedure for the synthesis of Compound 1 was carried out in such a manner that Compound I-1 was replaced with Compound I-2(22.40 g, 1 equivalent, 0.1mol), and the proportions of the respective starting materials were adjusted to obtain Compound 3(35.24 g, yield 81%).
Elemental analysis: c30H17N3Theoretical value of O: c, 82.74; h, 3.93; n, 9.65; measured value: c, 82.75; h, 3.95; n, 9.62; HRMS (ESI) M/z (M)+): theoretical value: 435.1372, respectively; measured value: 435.1377.
synthesis example 4
The synthetic route for compound 4 is shown below:
the synthesis route of intermediate 5-E' is the same as that of example 2.
The preparation method of the compound 4 specifically comprises the following steps:
(1) - (5) same as example 2;
(6) synthesis of Compound 4:
the same procedure as used for the synthesis of compound 1, except that intermediate 5-E' (29.11 g, 1 eq, 0.1mol) was used instead of intermediate 5-E and compound I-2(22.40 g, 1 eq) was used instead of compound I-1, with the remainder of the starting materials adjusted to give compound 4(35.68 g, 82% yield).
Elemental analysis: c30H17N3Theoretical value of O: c, 82.74; h, 3.93; n, 9.65; measured value: c, 82.71; h, 3.95; n, 9.66; HRMS (ESI) M/z (M)+): theoretical value: 435.1372, respectively; measured value: 435.1366.
synthesis example 5
The synthetic route for compound 5 is shown below:
the synthesis route of intermediate 5-E is the same as in example 1.
The preparation method of the compound 5 specifically comprises the following steps:
(1) - (5) same as in example 1;
(6) synthesis of Compound 5:
the procedure for the synthesis of Compound 1 was carried out in such a manner that Compound I-3(47.61 g, 1 equivalent, 0.1mol) was used in place of Compound I-1, and the proportions of the respective starting materials were adjusted to obtain Compound 5(53.60 g, yield 78%).
Elemental analysis: c49H29N5Theoretical value: c, 85.57; h, 4.25; n, 10.18; measured value: c, 85.58; h, 4.26; n, 10.16; HRMS (ESI) M/z (M)+): theoretical value: 687.2423, respectively; measured value: 687.2429.
synthesis example 6
The synthetic route for compound 6 is shown below:
the synthesis route of intermediate 5-E' is the same as that of example 2.
The preparation method of the compound 6 specifically comprises the following steps:
(1) - (5) same as example 2;
(6) synthesis of Compound 6:
the same procedure as used for the synthesis of compound 1, except that intermediate 5-E' (29.11 g, 1 eq, 0.1mol) was used instead of intermediate 5-E and compound I-3(47.61 g, 1 eq) was used instead of compound I-1, with the remainder of the starting materials adjusted to give compound 6(35.68 g, 52% yield).
Elemental analysis: c49H29N5Theoretical value: c, 85.57; h, 4.25; n, 10.18; measured value: c, 85.58; h, 4.25; n, 10.17; HRMS (ESI) M/z (M)+): theoretical value: 687.2423, respectively; measured value: 687.2428.
synthesis example 7
The synthetic route for compound 7 is shown below:
the synthesis route of intermediate 5-E is the same as in example 1.
The preparation method of the compound 7 specifically comprises the following steps:
(1) - (5) same as in example 1;
(6) synthesis of compound 7:
the procedure for the synthesis of compound 1 was followed except that compound I-4(32.41 g, 1 eq, 0.1mol) was used in place of compound I-1, and the proportions of the starting materials were adjusted to give compound 7(47.49 g, 82% yield).
Elemental analysis: c41H26Theoretical NOP value: c, 84.96; h, 4.52; n, 2.42; measured value: c, 84.99; h, 4.51; n, 2.40; HRMS (ESI) M/z (M)+): theoretical value: 579.1752, respectively; measured value: 579.1747.
synthesis example 8
The synthetic route for compound 8 is shown below:
the synthesis route of intermediate 5-E' is the same as that of example 2.
The preparation method of the compound 8 specifically comprises the following steps:
(1) - (5) same as example 2;
(6) synthesis of compound 8:
the same procedure as used for the synthesis of Compound 1, except that intermediate 5-E' (29.11 g, 1 eq, 0.1mol) was used instead of intermediate 5-E and Compound I-4(1 eq, 0.1mol) was used instead of Compound I-1, with the remainder of the starting materials being adjusted to give Compound 8(48.07 g, 83% yield).
Elemental analysis: c41H26Theoretical NOP value: c, 84.96; h, 4.52; n, 2.42; measured value: c, 84.98; h, 4.51; n, 2.41; HRMS (ESI) M/z (M)+): theoretical value: 579.1752, respectively; measured value: 579.1759.
synthesis example 9
The synthetic route for compound 9 is shown below:
the synthesis route of intermediate 5-E is the same as in example 1.
The preparation method of the compound 9 specifically comprises the following steps:
(1) - (5) same as in example 1;
(6) synthesis of compound 9:
the procedure for the synthesis of Compound 1 was followed except that Compound I-1 was replaced with Compound I-5(32.19 g, 1 equivalent, 0.1mol), and the proportions of the starting materials were adjusted to give Compound 9(42.65 g, 80% yield).
Elemental analysis: c35H19NO3Theoretical value of S: c, 78.78; h, 3.59; n, 2.62; measured value: c, 78.80; h, 3.58; n, 2.63; HRMS (ESI) M/z (M)+): theoretical value: 533.1086, respectively; measured value: 533.1088.
synthesis example 10
The synthetic route for compound 10 is shown below:
the synthesis route of intermediate 5-E' is the same as that of example 2.
The preparation method of the compound 10 specifically comprises the following steps:
(1) - (5) same as example 2;
(6) synthesis of compound 10:
the same procedure as used for the synthesis of compound 1, except that intermediate 5-E' (29.11 g, 1 eq, 0.1mol) was used instead of intermediate 5-E and compound I-5(32.19 g, 1 eq) was used instead of compound I-1, with the proportions of the remaining starting materials adjusted to give compound 10(42.11 g, 79% yield).
Elemental analysis: c35H19NO3Theoretical value of S: c, 78.78; h, 3.59; n, 2.62; measured value: c, 78.80; h, 3.58; n, 2.63; HRMS (ESI) M/z (M)+): theoretical value: 533.1086, respectively; measured value: 533.1092.
synthesis example 11
The synthetic route for compound 11 is shown below:
the synthesis route of intermediate 5-E is the same as in example 1.
The preparation method of the compound 11 specifically comprises the following steps:
(1) - (5) same as in example 1;
(6) synthesis of compound 11:
the procedure for the synthesis of Compound 1 was followed except that Compound I-6(23.20 g, 1 equivalent, 0.1mol) was used in place of Compound I-1, and the proportions of the starting materials were adjusted to give Compound 11(35.46 g, 80% yield).
Elemental analysis: c34H21N theoretical value: c, 92.07; h, 4.77; n, 3.16; measured value: c, 92.08; h, 4.78; n, 3.14; HRMS (ESI) M/z (M)+): theoretical value: 443.1674, respectively; measured value: 443.1677.
synthesis example 12
The synthetic route for compound 12 is shown below:
the synthesis route of intermediate 5-E' is the same as that of example 2.
The preparation method of the compound 12 specifically comprises the following steps:
(1) - (5) same as example 2;
(6) synthesis of compound 12:
the same procedure as used for the synthesis of compound 1, except that intermediate 5-E' (29.11 g, 1 eq, 0.1mol) was used instead of intermediate 5-E and compound I-6(23.20 g, 1 eq) was used instead of compound I-1, with the remainder of the starting materials adjusted to give compound 12(42.11 g, 79% yield).
Elemental analysis: c34H21N theoretical value: c, 92.07; h, 4.77; n, 3.16; measured value: c, 92.09; h, 4.78; n, 3.13; HRMS (ESI) M/z (M)+): theoretical value: 443.1674, respectively; measured value: 443.1683.
synthesis example 13
The synthetic route for compound 13 is shown below:
the synthesis route of intermediate 5-E is the same as in example 1.
The preparation method of the compound 13 specifically comprises the following steps:
(1) - (5) same as in example 1;
(6) synthesis of compound 13:
the procedure for synthesizing Compound 1 was carried out in such a manner that Compound I-7(36.00 g, 1 equivalent, 0.1mol) was used in place of Compound I-1, and the proportions of the respective starting materials were adjusted to obtain Compound 13(43.41 g, yield 76%).
Elemental analysis: c42H25N3Theoretical value: c, 88.24; h, 4.41; n, 7.35; measured value: c, 88.23; h, 4.40; n, 7.37; HRMS (ESI) M/z (M)+): theoretical value: 571.2048, respectively; measured value: 571.2054.
fig. 1 is a graph showing the theoretical calculation results of the HOMO level, LUMO level, and energy band gap Eg of compound 13.
Synthesis example 14
The synthetic route for compound 14 is shown below:
the synthesis route of intermediate 5-E' is the same as that of example 2.
The preparation method of the compound 14 specifically comprises the following steps:
(1) - (5) same as example 2;
(6) synthesis of compound 14:
the same procedure as used for the synthesis of compound 1, except that intermediate 5-E' (29.11 g, 1 eq, 0.1mol) was used instead of intermediate 5-E and compound I-7(36.00 g, 1 eq) was used instead of compound I-1, with the remainder of the starting materials adjusted to give compound 14(43.98 g, 77% yield).
Elemental analysis: c42H25N3Theoretical value: c, 88.24; h, 4.41; n, 7.35; measured value: c, 88.22; h, 4.42; n, 7.36; HRMS (ESI) M/z (M)+): theoretical value: 571.2048, respectively; measured value: 571.2055.
synthesis example 15
The synthetic route for compound 15 is shown below:
the synthesis route of intermediate 5-E is the same as in example 1.
The preparation method of the compound 15 specifically comprises the following steps:
(1) - (5) same as in example 1;
(6) synthesis of compound 15:
the procedure for the synthesis of Compound 1 was followed except that Compound I-1 was replaced with Compound I-8(46.31 g, 1 equivalent, 0.1mol), and the proportions of the starting materials were adjusted to give Compound 15(50.57 g, 75% yield).
Elemental analysis: c49H30N4Theoretical value: c, 87.22; h, 4.48(ii) a N, 8.30; measured value: c, 87.24; h, 4.50; n, 8.30; HRMS (ESI) M/z (M)+): theoretical value: 674.2470, respectively; measured value: 674.2477.
synthesis example 16
The synthetic route for compound 16 is shown below:
the synthesis route of intermediate 5-E' is the same as that of example 2.
The preparation method of the compound 16 specifically comprises the following steps:
(1) - (5) same as example 2;
(6) synthesis of compound 16:
the same procedure as used for the synthesis of compound 1, except that intermediate 5-E' (29.11 g, 1 eq, 0.1mol) was used instead of intermediate 5-E and compound I-8(46.31 g, 1 eq) was used instead of compound I-1, with the remainder of the starting materials adjusted to give compound 16(52.60 g, 78% yield).
Elemental analysis: c49H30N4Theoretical value: c, 87.22; h, 4.48; n, 8.30; measured value: c, 87.23; h, 4.50; n, 8.27; HRMS (ESI) M/z (M)+): theoretical value: 674.2470, respectively; measured value: 674.2467.
synthesis example 17
The synthetic route for compound 17 is shown below:
the synthesis route of intermediate 5-E is the same as in example 1.
The preparation method of the compound 17 specifically comprises the following steps:
(1) - (5) same as in example 1;
(6) synthesis of compound 17:
the procedure for the synthesis of Compound 1 was followed except that Compound I-1 was replaced with Compound I-9(31.10 g, 1 equivalent, 0.1mol), and the proportions of the starting materials were adjusted to give Compound 17(39.17 g, 75% yield).
Elemental analysis: c37H22N4Theoretical value: c, 85.04; h, 4.24; n, 10.72; measured value: c, 85.05; h, 4.24; n, 10.71; HRMS (ESI) M/z (M)+): theoretical value: 522.1844, respectively; measured value: 522.1851.
synthesis example 18
The synthetic route for compound 18 is shown below:
the synthesis route of intermediate 5-E' is the same as that of example 2.
The preparation method of the compound 18 specifically comprises the following steps:
(1) - (5) same as example 2;
(6) synthesis of compound 18:
the same procedure as used for the synthesis of compound 1, except that intermediate 5-E' (29.11 g, 1 eq, 0.1mol) was used instead of intermediate 5-E and compound I-9(31.10 g, 1 eq) was used instead of compound I-1, with the remainder of the starting materials adjusted to give compound 18(39.17 g, 75% yield).
Elemental analysis: c37H22N4Theoretical value: c, 85.04; h, 4.24; n, 10.72; measured value: c, 85.05; h, 4.23; n, 10.72; HRMS (ESI) M/z (M)+): theoretical value: 522.1844, respectively; measured value: 522.1839.
synthetic example 19
The synthetic route for compound 19 is shown below:
wherein the synthetic route of the intermediate 5-F is shown as follows:
the preparation method of the compound 19 specifically comprises the following steps:
(1) synthesis of intermediates 1-F:
the difference of the synthesis method of the intermediate 1-E is that 1-tert-butyl-3-bromo-4 iodobenzene (33.79 g, 1 equivalent, 0.1mol) is used to replace o-bromoiodobenzene, the proportion of the raw materials is adjusted to obtain the intermediate 1-F (23.64 g, 71% yield)
(2) Synthesis of intermediate 2-F:
the difference of the method is that the intermediate 1-F (33.30 g, 1 equivalent, 0.1mol) is used to replace the intermediate 1-E, and the ratio of each raw material is adjusted to obtain the intermediate 2-F.
(3) Synthesis of intermediate 3-F:
the difference from the synthesis of intermediate 3-E is that intermediate 2-F (1 eq, 0.1mol) was used instead of intermediate 2-E, and the proportions of the starting materials were adjusted to give intermediate 3-F (26.17 g, 57% yield).
(4) Synthesis of intermediate 4-F:
the difference from the synthesis of intermediate 4-E is that intermediate 3-F (45.91 g, 1 eq, 0.1mol) was used instead of intermediate 3-E, and the proportions of the starting materials were adjusted to give intermediate 4-F (20.10 g, 53% yield).
(5) Synthesis of intermediate 5-F:
the same synthesis method as intermediate 5-E was used, except that intermediate 4-F (37.92 g, 1 eq, 0.1mol) was used instead of intermediate 4-E, and the proportions of the starting materials were adjusted to give intermediate 5-F (27.43 g, 79% yield).
(6) Synthesis of compound 19:
the procedure was followed using compound I-7(36.00 g, 1 eq, 0.1mol) instead of compound I-1 and intermediate 5-F (34.72 g, 1 eq) instead of intermediate 5-E to synthesize Compound 1, with the proportions of the starting materials adjusted to give Compound 19(51.44 g, 82% yield).
Elemental analysis: c46H33N3Theoretical value: c, 88.01; h, 5.30; n, 6.69; measured value: c, 88.05; h, 5.28; n, 6.67; HRMS (ESI) M/z (M)+): theoretical value: 627.2674, respectively; measured value: 627.2678.
synthesis example 20
The synthetic route for compound 20 is shown below:
wherein, the synthetic route of the intermediate 5-F' is shown as follows:
the preparation method of the compound 20 specifically comprises the following steps:
(1) synthesis of intermediate 1-F':
the difference of the synthesis method is that 1-tert-butyl-4, 5-dibromonaphthalene (34.19 g, 1 equivalent, 0.1mol) is used for replacing o-bromoiodobenzene, the proportion of the raw materials is adjusted to obtain an intermediate 1-F' (21.84 g, the yield is 57%)
(2) Synthesis of intermediate 2-F':
the difference of the method is that the intermediate 1-F '(38.31 g, 1 equivalent, 0.1mol) is used to replace the intermediate 1-E, and the ratio of each raw material is adjusted to obtain the intermediate 2-F'.
(3) Synthesis of intermediate 3-F':
the difference from the synthesis of intermediate 3-E is that intermediate 2-F '(1 equivalent, 0.1mol) was used instead of intermediate 2-E, and the proportions of the starting materials were adjusted to give intermediate 3-F' (26.63 g, 58% yield).
(4) Synthesis of intermediate 4-F':
the difference from the synthesis of intermediate 4-E is that intermediate 3-F '(45.91 g, 1 eq, 0.1mol) was used instead of intermediate 3-E, and the proportions of the starting materials were adjusted to give intermediate 4-F' (21.24 g, 56% yield).
(5) Synthesis of intermediate 5-F':
the same synthesis method as intermediate 5-E was used, except that intermediate 4-F '(37.92 g, 1 equivalent, 0.1mol) was used instead of intermediate 4-E, and the proportions of the respective starting materials were adjusted to give intermediate 5-F' (28.12 g, 81% yield).
(6) Synthesis of compound 20:
the procedure was followed except that compound I-7(36.00 g, 1 eq, 0.1mol) was used instead of compound I-1 and intermediate 5-F' (34.72 g, 1 eq) was used instead of intermediate 5-E to prepare compound 20(50.81 g, 81% yield) by adjusting the proportions of the starting materials.
Elemental analysis: c46H33N3Theoretical value: c, 88.01; h, 5.30; n, 6.69; measured value: c, 88.03; h, 5.29; n, 6.68; HRMS (ESI) M/z (M)+): theoretical value: 627.2674, respectively; measured value: 627.2670.
synthesis example 21
The synthetic route for compound 21 is shown below:
wherein the synthetic route of the intermediate 5-G is shown as follows:
the preparation method of the compound 21 specifically comprises the following steps:
(1) synthesis of intermediates 1-G:
the difference of the synthesis method is that 2-bromo-3-iodonaphthalene (33.19G, 1 equivalent, 0.1mol) is used for replacing o-bromoiodobenzene, the proportion of the raw materials is adjusted, and the intermediate 1-G (19.29G, 59% of yield) is obtained
(2) Synthesis of intermediates 2-G:
the difference of the method is that the intermediate 1-E is replaced by the intermediate 1-G (32.70G, 1 equivalent, 0.1mol), and the ratio of each raw material is adjusted to obtain the intermediate 2-G.
(3) Synthesis of intermediate 3-G:
the difference from the synthesis of intermediate 3-E is that intermediate 2-G (1 eq, 0.1mol) was used instead of intermediate 2-E, and the proportions of the starting materials were adjusted to give intermediate 3-G (23.10G, 51% yield).
(4) Synthesis of intermediate 4-G:
the difference from the synthesis of intermediate 4-E is that intermediate 3-E was replaced with intermediate 3-G (45.30G, 1 eq, 0.1mol), and the proportions of the starting materials were adjusted to give intermediate 4-G (19.40G, 52% yield).
(5) Synthesis of intermediate 5-G:
the same procedure as for the synthesis of intermediate 5-E was followed except that intermediate 4-G (37.31G, 1 eq, 0.1mol) was used instead of intermediate 4-E, and the proportions of the starting materials were adjusted to give intermediate 5-G (27.29G, 80% yield).
(6) Synthesis of compound 21:
the procedure was followed for the synthesis of compound 1 except that compound I-9 (31.10G, 1 eq, 0.1mol) was used instead of compound I-1 and intermediate 5-G (34.11G, 1 eq) was used instead of intermediate 5-E, and the proportions of the starting materials were adjusted to give compound 21 (41.20G, 72% yield).
Elemental analysis: c41H24N4Theoretical value: c, 85.99; h, 4.22; n, 9.78; measured value: c, 85.98; h, 4.23; n, 9.78; HRMS (ESI) M/z (M)+): theoretical value: 572.2001, respectively; measured value: 572.2007.
synthesis example 22
The synthetic route for compound 22 is shown below:
wherein, the synthetic route of the intermediate 5-G' is shown as follows:
the preparation method of the compound 22 specifically comprises the following steps:
(1) synthesis of intermediate 1-G':
the difference of the synthesis method of the intermediate 1-E is that 1, 10-dibromobenzonaphthalene (33.59G, 1 equivalent and 0.1mol) is used for replacing o-bromoiodobenzene, and the proportion of the raw materials is adjusted to obtain the intermediate 1-G' (19.98G and 53 percent of yield)
(2) Synthesis of intermediate 2-G':
the difference of the method is that the intermediate 1-E is replaced by the intermediate 1-G '(37.70G, 1 equivalent, 0.1mol), and the ratio of each raw material is adjusted to obtain the intermediate 2-G'.
(3) Synthesis of intermediate 3-G':
the difference from the synthesis of intermediate 3-E is that intermediate 2-G '(1 eq, 0.1mol) is used instead of intermediate 2-E, and o-dibromobenzene (23.59G, 1 eq) is used instead of 1, 8-dibromonaphthalene, and the proportions of the raw materials are adjusted to obtain intermediate 3-G' (23.56G, 52% yield).
(4) Synthesis of intermediate 4-G':
the difference from the synthesis of intermediate 4-E is that intermediate 3-E was replaced by intermediate 3-G '(45.30G, 1 eq, 0.1mol), and the proportions of the starting materials were adjusted to give intermediate 4-G' (22.01G, 59% yield).
(5) Synthesis of intermediate 5-G':
the same synthesis method as intermediate 5-E was used, except that intermediate 4-G '(37.31G, 1 eq, 0.1mol) was used instead of intermediate 4-E, and the proportions of the starting materials were adjusted to give intermediate 5-G' (27.63G, 81% yield).
(6) Synthesis of compound 22:
the procedure was followed for the synthesis of compound 1 except that compound I-9 (31.10G, 1 eq, 0.1mol) was used instead of compound I-1 and intermediate 5-G' (34.11G, 1 eq) was used instead of intermediate 5-E, and the proportions of the starting materials were adjusted to give compound 22 (41.20G, 72% yield).
Elemental analysis: c41H24N4Theoretical value: c, 85.99; h, 4.22; n, 9.78; measured value: c, 85.98; h, 4.24; n, 9.77; HRMS (ESI) M/z (M)+): theoretical value: 572.2001, respectively; measured value: 572.2011.
synthesis example 23
The synthetic route for compound 23 is shown below:
wherein the synthetic route of the intermediate 5-H is shown as follows:
the preparation method of the compound 23 specifically comprises the following steps:
(1) synthesis of intermediates 1-H:
the difference of the synthesis method of the intermediate 1-E is that o-bromoiodobenzene (28.19 g, 1 equivalent and 0.1mol) is used for replacing o-bromoiodobenzene, and the proportion of the raw materials is adjusted to obtain the intermediate 1-H (18.56 g, 67 percent of yield)
(2) Synthesis of intermediate 2-H:
the difference of the method is that the intermediate 1-E is replaced by the intermediate 1-H (1 equivalent, 0.1mol), and the intermediate 2-H is obtained by adjusting the proportion of the raw materials.
(3) Synthesis of intermediate 3-H:
the difference from the intermediate 3-E synthesis method is that the intermediate 2-H (1 equivalent, 0.1mol) is used to replace the intermediate 2-E, 1, 8-dibromo-3, 6-diphenylnaphthalene (43.79 g, 1 equivalent) to replace 1, 8-dibromonaphthalene, and the raw materials are adjusted in proportion to obtain the intermediate 3-H (28.31 g, 51% yield).
(4) Synthesis of intermediate 4-H:
the difference from the synthesis of intermediate 4-E was that intermediate 3-E was replaced with intermediate 3-H (1 eq, 0.1mol), and the proportions of the starting materials were adjusted to give intermediate 4-H (24.71 g, 52% yield).
(5) Synthesis of intermediate 5-H:
the same synthesis as intermediate 5-E was followed except that intermediate 4-H (1 eq, 0.1mol) was used instead of intermediate 4-E, and the proportions of the starting materials were adjusted to give intermediate 5-H (35.46 g, 80% yield).
(6) Synthesis of compound 23:
the procedure was followed using compound I-2(22.40 g, 1 eq, 0.1mol) instead of compound I-1 and intermediate 5-H (44.32 g, 1 eq) instead of intermediate 5-E to synthesize Compound 1, with the proportions of the starting materials adjusted to give Compound 23(42.28 g, 72% yield).
Elemental analysis: c42H25N3Theoretical value of O: c, 85.84; h, 4.29; n, 7.15; measured value: c, 85.85；H，4.30；N，7.13；HRMS(ESI)m/z(M+): theoretical value: 587.1998, respectively; measured value: 587.1994.
synthesis example 24
The synthetic route for compound 24 is shown below:
wherein the synthetic route of the intermediate 5-H' is shown as follows:
the preparation method of the compound 24 specifically comprises the following steps:
(1) synthesis of intermediate 1-H':
the difference of the synthesis method is that 1, 8-dibromo naphthalene (1 equivalent and 0.1mol) is used for replacing o-bromoiodobenzene, the proportion of the raw materials is adjusted, and the intermediate 1-H' (18.64 g and 57 percent of yield) is obtained
(2) Synthesis of intermediate 2-H':
the difference of the method is that the intermediate 1-E is replaced by the intermediate 1-H '(32.70 g, 1 equivalent, 0.1mol), and the ratio of each raw material is adjusted to obtain the intermediate 2-H'.
(3) Synthesis of intermediate 3-H':
the difference from the synthesis of intermediate 3-E is that intermediate 2-H '(1 eq, 0.1mol) was used instead of intermediate 2-E, 1, 2-dibromo-4, 5-diphenylbenzene (38.79 g, 1 eq) instead of 1, 8-dibromonaphthalene, and the proportions of the starting materials were adjusted to give intermediate 3-H' (28.87 g, 52% yield).
(4) Synthesis of intermediate 4-H':
the same synthesis method as intermediate 4-E was used, except that intermediate 3-H '(55.51 g, 1 eq, 0.1mol) was used instead of intermediate 3-E, and the proportions of the starting materials were adjusted to give intermediate 4-H' (28.04 g, 59% yield).
(5) Synthesis of intermediate 5-H':
the same synthesis method as intermediate 5-E was used, except that intermediate 4-H '(47.52 g, 1 eq, 0.1mol) was used instead of intermediate 4-E, and the proportions of the starting materials were adjusted to give intermediate 5-H' (37.23 g, 84% yield).
(6) Synthesis of compound 24:
the procedure was followed using compound I-2(22.40 g, 1 eq, 0.1mol) instead of compound I-1 and intermediate 5-H' (44.32 g, 1 eq) instead of intermediate 5-E to synthesize Compound 1, with the proportions of the starting materials adjusted to give Compound 24(41.10 g, 70% yield).
Elemental analysis: c42H25N3Theoretical value of O: c, 85.84; h, 4.29; n, 7.15; measured value: c, 85.85; h, 4.30; n, 7.13; HRMS (ESI) M/z (M)+): theoretical value: 587.1998, respectively; measured value: 587.1990.
synthetic example 25
The synthetic route for compounds I-C-1 is shown below:
the preparation method of the compound I-C-1 specifically comprises the following steps:
(1) synthesis of intermediate 1-I-C-1:
a500 ml two-neck round bottom flask is taken and put into a stirrer and an upper reflux pipe, nitrogen is filled after drying, and ortho-nitrobenzeneboronic acid (16.70 g, 1 equivalent, 0.1mol), ortho-bromoiodobenzene (28.19 g, 1.0 equivalent, 01mol) and potassium carbonate (K) are respectively added2CO31.5 equivalents), ethanol (50 ml), water (50 ml), toluene (200 ml) and tetrakis (triphenylphosphine) palladium (Pd (PPh)3)40.05 eq), heated to reflux and reacted for 12 hours, cooled to room temperature after completion of the reaction, quenched by addition of 200 ml of water, extracted with dichloromethane (3 × 400 ml), the resulting extract was dried over magnesium sulfate, filtered and spun-dried in that order, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (vol.%)) to give intermediate 1-i-C-1 (17.45 g, 63% yield).
(2) Synthesis of intermediate 2-I-C-1:
a500 ml two-neck round-bottom flask was taken, a stirrer and an upper reflux tube were placed in the flask, nitrogen was introduced after drying, and the intermediates 1-I-C-1 (27.70 g, 1 eq, 0.1mol), bis (pinacolato) diboron (25.41 g, 1 eq), potassium acetate (potassium acetate, 19.61 g, 2 eq), (1, 1' -bis (diphenylphosphino) ferrocene) dichloropalladium (II) (Pd (dppf) Cl) were added20.025 eq) and 1, 4-dioxane (200 ml) at 120 ℃ for 8 h, after completion of the reaction, cooled to room temperature, quenched with water, extracted with dichloromethane (200 ml. times.3), the extracts dried over anhydrous magnesium sulphate, spun dry and the crude product isolated by silica gel column chromatography to give intermediate 2-I-C-1 (19.84 g, 61% yield).
(3) Synthesis of intermediate 3-I-C-1:
taking a 500 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding an intermediate 2-I-C-1 (1 equivalent, 0.1mol), 1, 8-dibromonaphthalene (28.59 g, 1 equivalent, 0.1mol) and potassium carbonate (K)2CO31.5 equivalents), ethanol (25 ml), water (25 ml), toluene (100 ml) and tetrakis (triphenylphosphine) palladium (Pd (PPh)3)40.05 eq), the mixture was refluxed for 12 hours, after the reaction was cooled to room temperature, water was added to the reaction system, extraction was performed with dichloromethane, the obtained extract was dried over magnesium sulfate, filtered and dried by rotation, and the crude product was purified by chromatography (ethyl acetate/hexane, 1/10) to obtain intermediate 3-i-C-1 (23.37 g, 58% yield).
(4) Synthesis of intermediate 4-I-C-1:
taking a 500 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding an intermediate 3-I-C-1 (40.30 g, 1 equivalent, 0.1mol) and dichlorobis (tricyclohexylphosphine) palladium (PdCl)2(PCy3)23.69 g, 0.05 eq), pivalic acid (t-BuCO)2H, 2 equivalents), cesium carbonate (Cs)2CO32 eq) and dimethylacetamide (200 ml) at 120 ℃ for 10 hours, cooling to room temperature after completion of the reaction, concentrating the reaction and chromatographically purifying the crude product (ethyl acetate/hexane, 1/10) to giveIntermediate 4-I-C-1 (25.44 g, 78.74% yield).
(5) Synthesis of intermediate 5-I-C-1:
a500 ml double-neck round-bottom bottle is taken and placed into a stirrer and an upper reflux pipe, nitrogen is filled after drying, 4-I-C-1 (32.31 g, 1 equivalent), triphenylphosphine (2 equivalents) and 1, 2-dichlorobenzene (100 ml) are respectively added, heating is carried out at 180 ℃ for 12 hours, cooling is carried out to room temperature after the reaction is finished, the reaction system is concentrated, and the crude product is purified by chromatography (ethyl acetate/hexane, 1/10) to obtain an intermediate 5-I-C-1 (23.29 g, yield 80%).
(6) Synthesis of Compound I-C-1
Taking a 500 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding an intermediate 5-I-C-1 (29.11 g, 1 equivalent, 0.1mol), 2-bromo-3 phenylquinoxaline (1 equivalent, 0.1mol), cesium carbonate (3 equivalent), and tris (dibenzylideneacetone) dipalladium (Pd)2(dba)30.05 eq) and 2-dicyclohexylphosphonium-2 ', 4', 6 ' -triisopropylbiphenyl (xphos, 42.32 g, 0.05 eq), then toluene was added, the mixture was refluxed for 24 hours, cooled to room temperature after the reaction, the reaction was filtered and concentrated, and the crude product was purified by chromatography (ethyl acetate/hexane, 1/10) to give compound i-C-1 (38.63 g, 78% yield).
Elemental analysis: c36H21N3Theoretical value: c, 87.25, H, 4.27, N, 8.48, found: c, 87.29, H, 4.26, N, 8.45, HRMS (ESI) M/z (M)+): theoretical value: 495.1735, found: 495.1739.
synthesis example 26
The synthetic route for compound II-I-C-1 is shown below:
the preparation method of the compound II-I-C-1 specifically comprises the following steps:
(1) synthesis of intermediate 1-II-I-C-1:
taking 500 ml of double necksPlacing a round-bottom flask into a stirrer and an upper reflux pipe, drying, introducing nitrogen, and adding o-nitrobenzeneboronic acid (16.70 g, 1 equivalent, 0.1mol), 1-bromo-8 iodonaphthalene (1 equivalent, 0.1mol), and potassium carbonate (K)2CO31.5 equivalents), ethanol (50 ml), water (50 ml), toluene (200 ml) and tetrakis (triphenylphosphine) palladium (Pd (PPh3)4, 0.05 equivalent), heated to reflux and reacted for 12 hours, cooled to room temperature after completion of the reaction, quenched by addition of 200 ml of water, extracted with dichloromethane (3 × 400 ml), the resulting extract was dried over magnesium sulfate, filtered and spun to dryness, and the crude product was purified by chromatography (ethyl acetate/hexane, 1/10), intermediate 1-ii-i-C-1 (22.56 g, 69% yield)
(2) Synthesis of intermediate 2-II-I-C-1:
a500 ml two-neck round-bottom flask was taken and placed with a stirrer and an upper reflux tube, after drying, nitrogen was introduced, and the intermediate 1-II-I-C-1 (32.70 g, 1 eq.), bisphenopinacol diboron (25.41 g, 1 eq.), potassium acetate (potassium acetate, 19.61 g, 2 eq.), and (1, 1' -bis (diphenylphosphino) ferrocene) dichloropalladium (II) (Pd (dppf) Cl) were added20.025 eq) and 1, 4-dioxane (200 ml) at 120 ℃ for 8 hours, after completion of the reaction, cooled to room temperature, quenched with water, extracted with dichloromethane (200 ml. times.3), the extract was dried over anhydrous magnesium sulphate, spun dry and the crude product was isolated by silica gel column chromatography to give intermediate 2-ii-i-C-1 (24.39 g, 65% yield).
(3) Synthesis of intermediate 3-II-I-C-1:
a500 ml two-neck round-bottom flask is taken and put into a stirrer and an upper reflux pipe, nitrogen is filled after drying, and an intermediate 2-II-I-C-1 (1 equivalent, 0.1mol), o-dibromobenzene (23.59 g, 1 equivalent, 0.1mol) and potassium carbonate (K) are respectively added2CO31.5 equivalents), ethanol (25 ml), water (25 ml), toluene (100 ml) and tetrakis (triphenylphosphine) palladium (Pd (PPh)3)40.05 eq), the mixture is refluxed for 12 hours, after the reaction is cooled to room temperature, water is added to the reaction system, extraction is carried out by dichloromethane, magnesium sulfate is added to the obtained extract liquid in sequence for drying, filtration and spin-drying, and the crude product is purified by chromatography (B)Ethyl acetate/hexanes, 1/10) to afford intermediate 3-ii-i-C-1 (22.17 g, 55% yield).
(4) Synthesis of intermediate 4-II-I-C-1:
taking a 500 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding an intermediate 3-II-I-C-1 (40.30 g, 1 equivalent) and dichlorobis (tricyclohexylphosphine) palladium (PdCl)2(PCy3)23.69 g, 0.05 eq), pivalic acid (t-BuCO)2H, 2 equivalents), cesium carbonate (Cs)2CO32 eq) and dimethylacetamide (200 ml) were stirred at 120 ℃ for 10 h, after completion of the reaction cooled to room temperature, the reaction was concentrated and the crude product was purified by chromatography (ethyl acetate/hexane, 1/10) to afford intermediate 4-ii-i-C-1 (16.16 g, 50% yield).
(5) Synthesis of intermediate 5-II-I-C-1:
a500 ml double-neck round-bottom bottle is taken, a stirrer and an upper reflux pipe are placed in the bottle, nitrogen is filled after drying, 4-II-I-C-1 (32.31 g, 1 equivalent), triphenylphosphine (2 equivalents) and 1, 2-dichlorobenzene (100 ml) are respectively added, heating is carried out at 180 ℃ for 12 hours, cooling is carried out to room temperature after the reaction is finished, the reaction system is concentrated, and a crude product is purified by chromatography (ethyl acetate/hexane, 1/10) to obtain an intermediate 5-II-I-C-1 (22.99 g, 79% of yield).
(6) Synthesis of Compound II-I-C-1
Taking a 500 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding an intermediate 5-II-I-C-1 (29.11 g, 1 equivalent, 0.1mol), a compound 2-bromo-3 phenylquinoxaline (30 g, 1 equivalent, 0.1mol), cesium carbonate (3 equivalent), tris (dibenzylideneacetone) dipalladium (Pd)2(dba)30.05 eq) and 2-dicyclohexylphosphonium-2 ', 4', 6 ' -triisopropylbiphenyl (xphos, 42.32 g, 0.05 eq), then toluene was added, the mixture was refluxed for 24 hours, cooled to room temperature after the reaction, the reaction was filtered and concentrated, and the crude product was purified by chromatography (ethyl acetate/hexane, 1/10) to give compound ii-i-C-1 (36.15 g, 73% yield).
Elemental analysis: c36H21N3Theoretical value: c, 87.25, H, 4.27, N, 8.48, found: c, 87.22, H, 4.28, N, 8.50, HRMS (ESI) M/z (M)+): theoretical value: 495.1735, found: 495.1742.
synthesis examples 27 to 56
The synthetic procedures for the compounds of synthetic examples 27 to 56 were the same as those for compounds I-C-1, with only partial substitution of starting materials, products, HRMS m/z (theoretical/actual measurement), elemental analysis results are shown in Table 1.
TABLE 1
Synthesis examples 57 to 88
The synthetic procedures for the compounds in synthetic examples 57 to 88 were carried out using the compounds II-I-C-1, with only partial substitution of the starting materials, products, HRMS m/z (theoretical/actual measurement), and elemental analysis results as shown in Table 2.
TABLE 2
Synthesis example 89
The synthetic route for compounds II-I-E-73 is shown below:
the preparation method of the compound II-I-E-73 specifically comprises the following steps:
(1) synthesis of intermediate 1-II-I-C-1:
a500 ml double-neck round-bottom bottle is taken and placed into a stirrer and an upper reflux pipe, nitrogen is filled after drying, an intermediate 5-II-I-C-1 (29.11 g, 1 equivalent, 0.1mol), N-bromosuccinimide (1.2 equivalent) and tetrahydrofuran (100 ml) are respectively added, stirring is carried out for 10 hours at room temperature, 5 ml of water is added after the reaction is finished, the reaction system is extracted for three times by dichloromethane, magnesium sulfate is sequentially added into obtained extract liquid for drying, filtering and spin-drying, and the crude product is purified by chromatography (ethyl acetate/hexane, 1/10) to obtain an intermediate 1-II-I-E-73 (25.83 g, the yield is 70%).
(2) Synthesis of intermediate 2-II-I-E-73:
taking a 500 ml double-neck round-bottom bottle, putting a stirrer and an upper reflux pipe, filling nitrogen after drying, and respectively adding an intermediate 1-II-I-E-73 (36.90 g, 1 equivalent, 0.1mol),
(35.31 g, 0.1mol), K2CO3(1.5 eq), ethanol (25 ml), water (25 ml), toluene (100 ml) and tetrakis (triphenylphosphine) palladium (0.05 eq) were refluxed for 12 hours, cooled to room temperature after the reaction, water was added to the reaction system, extraction was performed with dichloromethane, the obtained extract was dried over magnesium sulfate, filtered and spun to dryness, and the crude product was purified by chromatography (ethyl acetate/hexane, 1/10) to give intermediate 2-ii-i-E-73 (43.67 g, 73% yield).
(3) Synthesis of Compounds II-I-E-73:
synthesis of the same compounds I-C-1, using
(21.20 g, 1 eq, 0.1mol) instead of 2-bromo-3 phenylquinoxaline, the proportions of the starting materials were adjusted to give the compounds II-I-E-73 (48.91 g, 67% yield).
Elemental analysis: c53H38N4Theoretical value: c, 87.09; h, 5.24; n, 7.67; measured value: c, 87.05; h, 5.26; n, 7.69；HRMS(ESI)m/z(M+): theoretical value: 730.3096, respectively; measured value: 730.3089.
device embodiments
1. Device example 1
The present embodiment provides an organic electroluminescent device comprising an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7 and a cathode 8, which are sequentially stacked and disposed on a substrate 1, as shown in fig. 2.
The anode 2 is made of opaque ITO (ITO/Ag/ITO) material;
NDP-9 and NPB are selected as the hole injection layer 3, wherein the NDP-9: NPB ═ 3:97 (mass ratio);
the hole transport layer 4 is NPB;
the light-emitting layer 5 is composed of a host material and a doping material, the host material is the compound 1 synthesized in the synthesis example 1, the guest material is Ir (DBQ)2(acac), and the mass ratio of the host material to the guest material is 95: 5;
the electron transport layer 6 is selected from BPhen and LiQ, wherein BPhen: LiQ ═ 1:1 (mass ratio);
the electron injection layer 7 is LiQ;
the cathode 8 is Mg/Ag + CPL, wherein the ratio of Mg to Ag is 9:1 (mass ratio).
The preparation method of the organic electroluminescent device comprises the following steps:
(1) substrate cleaning: carrying out ultrasonic treatment on the glass substrate coated with the opaque ITO (ITO/Ag/ITO) in an aqueous cleaning agent (the components and concentration of the aqueous cleaning agent: glycol solvent is less than or equal to 10 wt%, and triethanolamine is less than or equal to 1 wt%), washing in deionized water, carrying out ultrasonic oil removal in a mixed solvent of acetone and ethanol (volume ratio is 1:1), baking in a clean environment until moisture is completely removed, and then cleaning with ultraviolet light and ozone to obtain the glass substrate with the anode layer;
(2) evaporation: placing the glass substrate with the anode layer in a vacuum chamber, and vacuumizing to 1 × 10-6～2×10-4Pa, evaporating a hole injection material on the anode layer in a co-evaporation mode in vacuum, adjusting the rate of NDP-9 and NPB according to the mass ratio, wherein the total evaporation rate is 0.1nm/s, and the evaporation thickness is 10 nm;
(3) a hole transport layer is evaporated on the hole injection layer, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 80 nm;
(4) evaporating a luminescent layer on the hole transport layer, and evaporating a luminescent host material and an object material in vacuum in a co-evaporation mode, wherein the evaporation rate of the host material and the object material is adjusted according to the mass ratio, the total evaporation rate is 0.01nm/s, and the total evaporation film thickness is 40 nm;
(5) vacuum evaporating an electron transport layer on the luminescent layer, and adjusting the evaporation rate according to the mass ratio, wherein the total evaporation rate is 0.1nm/s, and the total evaporation film thickness is 30 nm;
(6) vacuum evaporating an electron injection layer on the electron transport layer, wherein the evaporation rate is 0.05nm/s, and the total film thickness of the evaporation is 1 nm;
(7) and (3) performing vacuum evaporation on the electron injection layer to form Mg/Ag as a cathode layer of the device, wherein the evaporation rate is adjusted according to the mass ratio, the total evaporation rate is 0.1nm/s, the total evaporation film thickness is 20nm, and the CPL thickness on the Mg/Ag is 80 nm.
2. Device examples 2 to 89
Device examples 2 to 89 differ from device example 1 only in that the host materials in the light-emitting layer are different, and the host materials are the compounds synthesized in synthesis examples 2 to 89, respectively.
3. Comparative device example 1
Device comparative example 1 differs from device example 1 only in that the host material in the light-emitting layer is different, the host material being CBP.
Test example 1
Measurement of thermal decomposition temperature:
thermal decomposition temperature test of the fused ring compound material was carried out using a thermogravimetric analyzer (TATGA 55, USA) in a range of room temperature to 600 ℃ at a temperature rise rate of 10 ℃/min, and a temperature at which 5% of weight loss is defined as a thermal decomposition temperature (T) under a nitrogen atmosphered) The measurement results are shown in table 3:
TABLE 3
From the thermal decomposition temperatures of the compound materials obtained by the tests, the fused ring compound material provided by the invention has the decomposition temperature of 350-500 ℃, and meets the requirements of good thermal stability and proper sublimation temperature.
Test example 2
Testing of HOMO and LUMO energy levels:
the LUMO energy levels of the fused cyclic compound materials prepared in examples 1 to 26 were measured using an electrochemical workstation using cyclic voltammetry (CV shanghai chen CHI-600E) with a platinum wire (Pt) as a counter electrode and silver/silver chloride (Ag/AgCl) as a reference electrode. Under the nitrogen atmosphere, the test is carried out in methylene chloride electrolyte containing 0.1M tetrabutylammonium hexafluorophosphate at the scanning rate of 100mV/s, the potential calibration is carried out by ferrocene, and the absolute energy level of the potential of the ferrocene in the vacuum state is set as-4.8 eV:
HOMOenergy level＝-e(Eox-E1/2,ferrocene)+(-4.8)eV
LUMOEnergy level＝-e(Ere-E1/2,ferrocene)+(-4.8)eV
ET1(eV) triplet level.
EoxTo oxidation potential, EreTo reduce the potential, E1/2,ferroceneIs ferrocene oxidation potential. Triplet state energy levelAnd (3) testing conditions are as follows: fluorescence spectrophotometer (Hitachi F-4600), solution state (toluene as solvent, concentration 2 x 10)-5mol/L) and 78 degrees centigrade.
ET11240/shortest absorption wavelength
The measurement results are shown in table 4:
TABLE 4
According to the LUMO energy level and the HOMO energy level of each compound material obtained through the tests, the HOMO energy level and the LUMO energy level of the condensed ring compound material provided by the invention are completely separated, the energy gap width is reduced, the triplet state energy level is improved, and the energy backflow from the guest material to the host material is avoided, so that the luminous efficiency is reduced.
Test example 3
The following tests were carried out for the organic electroluminescent devices in some of the device examples provided by the present invention and in 1 device comparative example:
the characteristics of the device such as current, voltage, brightness, light-emitting spectrum and the like are synchronously tested by adopting a PR 650 spectrum scanning luminance meter and a KeithleyK 2400 digital source meter system, and the test conditions are as follows: the current density is 20mA/cm2Room temperature;
and (3) life test: the time (in hours) was recorded when the device brightness dropped to 95% of the original brightness.
The results are shown in Table 5.
TABLE 5
As can be seen from the test data in table 5, the fused ring compound provided by the present invention can effectively reduce the operating voltage of the device, increase the light emitting efficiency of the device, and prolong the device lifetime, compared with CBP, when used as the host material of the light emitting layer of the organic electroluminescent device.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (11)
1. A fused ring compound having a structure represented by formula (I) or formula (II):
R1-R14independently of one another, from hydrogen, deuterium, halogen, cyano, hydroxyl, nitro, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C60Alkyl, substituted or unsubstituted C2-C60Alkenyl of (a), substituted or unsubstituted C2-C60Alkynyl, substituted or unsubstituted C1-C60Alkylamino group of (A), substituted or unsubstituted C2-C60Substituted or unsubstituted C2-C60Alkynylamino, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C2-C60Alkenyloxy of (a), substituted or unsubstituted C2-C60Alkynyloxy of, substituted or unsubstituted C1-C60Thioalkoxy, substituted or unsubstituted C2-C60Thioalkenyloxy, substituted or unsubstituted C2-C60With a thioalkynyloxy group, substituted or unsubstituted C1-C60With an alkyl boron group, substituted or unsubstituted C2-C60Of alkenylboronRadical, substituted or unsubstituted C2-C60With a boron alkynyl group, substituted or unsubstituted C1-C60Ester group of (1), substituted or unsubstituted C1-C60Amide group of (A), substituted or unsubstituted C4-C60Aryl, substituted or unsubstituted C3-C60Heteroaryl, substituted or unsubstituted C4-C60Aryloxy group of (1), substituted or unsubstituted C4-C60With an aromatic amine group, substituted or unsubstituted C4-C60Thioaryloxy, substituted or unsubstituted C4-C60An arylboron group of, or
R1-R14Any two to four adjacent groups of which are linked to form one or more groups of rings A,
the ring A is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C60Aryl or substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring;
Ar1selected from substituted or unsubstituted groups P selected from:
C4-C60aryl of (C)3-C60Heteroaryl of (A), C4-C60Aryloxy group of (A), C4-C60Aromatic amine group of (2), C4-C60Thioaryloxy of (C)4-C60Aryl boron group of (A), C4-C60Aryl phosphine group of (A), C4-C60Heteroaryloxy of (A), C4-C60Heteroaromatic amino group of (1), C4-C60Thio-heteroaryloxy of (A), C4-C60Heteroaryl boron group of (A), C4-C60The heteroaromatic phosphine group of (1).
2. The fused ring compound of claim 1,
R1-R14independently of one another, from hydrogen, deuterium, halogen, cyano, hydroxyl, nitro, amino, amidino, hydrazineHydrazone, R23Substituted or unsubstituted C1-C60Alkyl of R23Substituted or unsubstituted C2-C60Alkenyl of R23Substituted or unsubstituted C2-C60Alkynyl of (A), R23Substituted or unsubstituted C1-C60Alkylamino group of (A), R23Substituted or unsubstituted C2-C60Of alkenylamino group, R23Substituted or unsubstituted C2-C60Alkynylamino of (a)23Substituted or unsubstituted C1-C60Alkoxy radical of (2), R23Substituted or unsubstituted C2-C60Alkenyloxy of (A), R23Substituted or unsubstituted C2-C60Alkynyloxy of (a), R23Substituted or unsubstituted C1-C60Thioalkoxy of, R23Substituted or unsubstituted C2-C60Thioalkenyloxy of (A), R23Substituted or unsubstituted C2-C60With a thioalkynyloxy group of23Substituted or unsubstituted C1-C60Of an alkyl group, R23Substituted or unsubstituted C2-C60Of an alkene boron group, R23Substituted or unsubstituted C2-C60With boron alkynyl, R23Substituted or unsubstituted C1-C60Ester group of (A), R23Substituted or unsubstituted C1-C60Amide group of (A), R23Substituted or unsubstituted C4-C60Aryl of (2), R23Substituted or unsubstituted C3-C60Heteroaryl of (A), R23Substituted or unsubstituted C4-C60Aryloxy group of R23Substituted or unsubstituted C4-C60Aromatic amine group of (2), R23Substituted or unsubstituted C4-C60Thioaryloxy of (A), R23Substituted or unsubstituted C4-C60An arylboron group of, or
R1-R14Any two to four adjacent groups of which are linked to form one or more groups of rings A,
the ring A is selected from R23Substituted or unsubstituted 3-to 7-memberedCarbocyclic ring, R23Substituted or unsubstituted 3-7 membered heterocyclic ring, R23Substituted or unsubstituted C4-C60Aryl or R of23Substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring;
Ar1selected from the group consisting of23A substituted or unsubstituted group P selected from:
C4-C60aryl of (C)3-C60Heteroaryl of (A), C4-C60Aryloxy group of (A), C4-C60Aromatic amine group of (2), C4-C60Thioaryloxy of (C)4-C60Aryl boron group of (A), C4-C60Aryl phosphine group of (A), C4-C60Heteroaryloxy of (A), C4-C60Heteroaromatic amino group of (1), C4-C60Thio-heteroaryloxy of (A), C4-C60Heteroaryl boron group of (A), C4-C60The hetero-aromatic phosphine group of (a),
R23independently of one another, from deuterium, halogen, nitro, cyano, R24Substituted or unsubstituted C1-C4Alkyl of R24Substituted or unsubstituted C1-C4Alkoxy radical of (2), R24Substituted or unsubstituted C1-C4Alkenyl of R24Substituted or unsubstituted C6-C12Aryl of (2), R24Substituted or unsubstituted C6-C12Aryloxy group of R24Substituted or unsubstituted C6-C12Of an arylamine group, R24Substituted or unsubstituted C3-C12Heteroaryl of (A), R24Substituted or unsubstituted C3-C12Preferably, R is23Independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, C1-C4Alkyl, halogen substituted C1-C4Alkyl, deuterium substituted C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4An alkenyl group of,Halogen substituted C1-C4Alkenyl, deuterium substituted C1-C4Alkenyl of, C6-C12Aryl of (C)6-C12Aryloxy group of (A), C6-C12Arylamino, halogen-substituted C6-C12Aryl, deuterium substituted C of6-C12Aryl of (C)3-C12Heteroaryl of (A), C3-C12A heteroaryl amine of (a), halogen-substituted C3-C12Heteroaryl, deuterium substituted C of3-C12The heteroaryl group of (a) is a group,
R24selected from deuterium, halogen, cyano, nitro.
3. The fused ring compound of claim 1,
R1-R14independently of one another, from deuterium, halogen, nitro, cyano, R23Substituted or unsubstituted groups as follows: c1-C4Alkyl of (C)2-C4Alkenyl of, C2-C4Alkynyl of (A), C1-C4Alkylamino group of (2), C2-C4Enamine group of (A), C2-C4Alkynylamino of (a), C1-C4Alkoxy group of (C)2-C4Alkenyloxy of (C)2-C4Alkynyloxy of (a), C1-C4Thioalkoxy of, C2-C4Thioalkenyloxy of (A), C2-C4Thioalkynyloxy of (C)1-C4Alkyl boron group of, C2-C4Of an alkenyl boron group, C2-C4Alkynyl boron group of C1-C4Ester group of (1), C1-C4Amide group of (1), C6-C20Aryl of (C)3-C20Heteroaryl of (A), C6-C20Aryloxy group of (A), C6-C20Aromatic amine group of (2), C6-C20Thioaryloxy of (C)6-C20The aromatic boron group of (a) is,
preferably, R1-R14Independently of one another, from hydrogen, deuterium, halogen, nitroRadical, cyano radical, C1-C4Alkyl, halogen substituted C1-C4Alkyl, deuterium substituted C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkenyl of (a), halogen-substituted C1-C4Alkenyl, deuterium substituted C1-C4Alkenyl of, C6-C12Aryl of (C)6-C12Aryloxy group of (A), C6-C12Arylamino, halogen-substituted C6-C12Aryl, deuterium substituted C of6-C12Aryl of (C)2-C12Heteroaryl of (A), C2-C12A heteroaryl amine of (a), halogen-substituted C2-C12Heteroaryl, deuterium substituted C of2-C12Or a heteroaryl group of
R1-R14Any two to four adjacent groups of which are linked to form one or more groups of rings A,
the ring A is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C12Aryl or substituted or unsubstituted C3-C12Said carbocycle is a saturated or unsaturated ring and said heterocycle is a saturated or unsaturated ring, preferably said ring A is selected from R23Substituted or unsubstituted 3-7 membered carbocyclic ring, R23Substituted or unsubstituted 3-7 membered heterocyclic ring, R23Substituted or unsubstituted C6-C12Aryl or R of23Substituted or unsubstituted C3-C12The carbocycle is a saturated or unsaturated ring, the heterocycle is a saturated or unsaturated ring,
preferably, R1-R14Independently of one another, from the group consisting of hydrogen, deuterium, halogen, methyl, ethyl, propyl, n-butyl, tert-butyl, trifluoromethyl, cyano, phenyl, biphenyl, terphenyl, pentalene, indenyl, naphthyl, azulene, heptalene, adamantyl, bornylene, triphenylene, indacenaphthylene, fluorenyl, spirobifluorenyl, benzofluorenyl, dibenzofluorenyl, phenalene, phenanthrenyl, trifluoromethyl, triphenylene,Anthracenyl, fluoranthenyl, benzophenanthrenyl, pyrenyl, chrysenyl, tetracenyl, picenyl, perylenyl, pentylphenyl, pentacenyl, rubicenyl, coronenyl, ovophenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, thienyl, furyl, quinolyl, carbazolyl, pyranyl, thiopyranyl, phthalazinyl, phenazinyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, indolyl, indolocarbazolyl, phenanthridinyl, acridinyl, perimidine, pteridinyl, quinazolinyl, quinoxalinyl, cinnolinyl, phenanthrolinyl, carbolinyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, dinaphthofuranyl, benzocarbazolyl, dibenzocarbazolyl, dibenzothiapyrrolyl, benzonaphthothiapyrrolyl, dinaphthothiazolyl, benzimidazolyl, imidazopyridinyl.
4. The fused ring compound of any one of claims 1 to 3,
Ar1is composed of
X1-X6Independently of one another, from N or CR15The number of N is 0 to 3,
it is shown that the connecting key is,
R15independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30Aryl boron group, substitutionOr unsubstituted C4-C30An aryl phosphorus group of, or
Two adjacent R15Are connected to form a ring B,
the ring B is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, the heterocycle is a saturated or unsaturated ring,
preferably, Ar1Is selected from
Q1-Q3Independently of one another, from N or CR21Preferably, Q1-Q3At least one of the N groups is N,
Q4-Q5independently of one another, from the group consisting of single bonds, NR21O, S, preferably Q4Is a single bond, Q5Is O, S or NR21Or Q4Is O, S or NR21，Q5Is a single bond, and is a single bond,
Q6-Q7are independently selected from N, CR21，
n5 is an integer of 0 to 2, n6 is an integer of 0 to 4,
L1selected from single bond, R25Substituted or unsubstituted C6-C60The aryl group of (a) is,
Ar2、R20、R21independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, R25Substituted or unsubstituted C1-C4Alkyl of R25Substituted or unsubstituted C2-C4Alkenyl of R25Substituted or unsubstituted C6-C30Aryl of (2), R25Substituted or unsubstituted C3-C30Heteroaryl of (A), R25Substituted or unsubstituted C6-C30Aryloxy group of R25Substituted or unsubstituted C6-C30Aromatic amine group of (2), R25Substituted or unsubstituted C3-C30Heteroaromatic amino group of (2), R25Substituted or unsubstituted C6-C30Thioaryloxy of (A), R25Substituted or unsubstituted C6-C30Aryl boron group of R25Substituted or unsubstituted C6-C30An aryl phosphorus group of, or
R20Two R not connected or adjacent to each other20Are connected to form a ring C,
the ring C is selected from R25Substituted or unsubstituted 3-7 membered carbocyclic ring, R25Substituted or unsubstituted 3-7 membered heterocyclic ring, R25Substituted or unsubstituted C6-C30Aryl or R of25Substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, the heterocycle is a saturated or unsaturated ring,
R25independently of one another, from deuterium, halogen, nitro, cyano, R26Substituted or unsubstituted C1-C4Alkyl of R26Substituted or unsubstituted C1-C4Alkoxy radical of (2), R26Substituted or unsubstituted C1-C4Alkenyl of R26Substituted or unsubstituted C6-C12Aryl of (2), R26Substituted or unsubstituted C6-C12Aryloxy group of R26Substituted or unsubstituted C6-C12Of an arylamine group, R26Substituted or unsubstituted C3-C12Heteroaryl of (A), R26Substituted or unsubstituted C3-C12The heteroaromatic amine group of (a) is,
R26selected from deuterium, halogen, cyano, nitro; or
Ar1Is selected from
It is shown that the connecting key is,
T1-T2independently of one another, selected from the group consisting of single bonds, O, S, SO2、CO、NR17、C(R17)2、POR17，
n1 is an integer of 0 to 3, n2 is an integer of 0 to 4, n3 is an integer of 0 to 3, n4 is an integer of 0 to 4,
R16independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30Arylboron group of (A), substituted or unsubstituted C4-C30An aryl phosphorus group of, or
Two adjacent R16Are connected to form a ring D,
the ring D is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, the heterocycle is a saturated or unsaturated ring,
R17independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30An arylboron group of, or
Two adjacent R17Are connected to form a ring E,
the ring E is selected from a substituted or unsubstituted cyclic 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring; or
Ar1Is composed of
Y1-Y5Independently of one another from NR18、CR18O or S, NR18The number of (a) is 0 to 3,
represents a single bond, and is a hydrogen atom,
R18independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30An arylboron group of, or
Two adjacent R18Are connected to form a ring F,
the ring F is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30The carbocyclic ring is a saturated or unsaturated ring, and the heterocyclic ring is a saturated or unsaturated ring.
5. A fused ring compound according to any one of claims 1 to 4,
Ar1selected from the group consisting of19A substituted or unsubstituted group G selected from:
the substituent R19Independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, C1-C4Alkyl, halogen substituted C1-C4Alkyl, deuterium substituted C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkenyl of (a), halogen-substituted C1-C4Alkenyl, deuterium substituted C1-C4Alkenyl of, C6-C12Aryl of (C)6-C12Aryloxy group of (A), C6-C12Arylamino, halogen-substituted C6-C12Aryl, deuterium substituted C of6-C12Aryl of (C)2-C12Heteroaryl of (A), C2-C12A heteroaryl amine of (a), halogen-substituted C2-C12Heteroaryl, deuterium substituted C of2-C12The heteroaryl group of (a);
preferably, the substituent R19Independently of one another, from hydrogen, deuterium, halogen, methyl, deuterated methyl, trifluoromethyl, ethyl, propyl, tert-butyl, or mixtures thereof,Cyano, vinyl, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, phenanthrenyl or grate, benzofuranyl, benzothienyl, carbazolyl,
wherein the content of the first and second substances,
indicating a bond, ＊ indicating a binding site.
6. A fused ring compound according to any one of claims 1 to 5,
Ar1selected from the group consisting of27A substituted or unsubstituted group M selected from:
R27independently of one another, from deuterium, halogen, cyano, nitro, C1-C4Alkyl, deuterium substituted C1-C4Alkyl, halogen substituted C1-C4Alkyl of (C)1-C4Alkenyl of, C6-C20Aryl, deuterium substituted C of6-C20Aryl, cyano-substituted C6-C20Aryl, halogen substituted C6-C20Aryl, trifluoromethyl substituted C6-C20Aryl of (C)3-C12Heteroaryl, deuterium substituted C of3-C12Heteroaryl, cyano-substituted C of3-C12Heteroaryl, halogen substituted C of3-C12Heteroaryl, trifluoromethyl substituted C of3-C12The heteroaryl group of (a) is a group,
wherein the content of the first and second substances,
it is shown that the connecting key is,
l is selected from a single bond, R28Substituted or unsubstituted C6-C20The aryl group of (a) is,
T1、T2independently of one another, from O, S, C (R)28)2、NR28，
R28Independently of one another, from hydrogen, deuterium, halogen, cyano, nitro, R29Substituted or unsubstituted C1-C4Alkyl of R29Substituted or unsubstituted C6-C12The aryl group of (a) is,
R29selected from deuterium, halogen, cyano, nitro,
preferably, R28Independently of one another, from the group consisting of methyl, phenyl, deuterated methyl, deuterated phenyl, halogen-substituted methyl, halogen-substituted phenyl.
7. A fused ring compound according to any one of claims 1 to 6, wherein Ar is Ar1Are electron withdrawing groups.
8. The fused ring compound of any of claims 1-7, having a molecular structure as shown in any one of:
9. a process for the preparation of a fused ring compound as claimed in any one of claims 1 to 8,
the synthesis steps of the compound shown in the formula (I) are as follows:
taking a compound shown in a formula (A) and a compound shown in a formula (B) as initial raw materials, and carrying out Suzuki coupling reaction to obtain an intermediate 1-A; reacting the intermediate 1-A with a compound shown as a formula (C) to obtain an intermediate 2-A; carrying out coupling reaction on the intermediate 2-A and a compound shown as a formula (D) to obtain an intermediate 3-A; carrying out coupling and ring-closing reaction on the intermediate 3-A to obtain an intermediate 4-A; carrying out nitro reduction and ring closure reaction on the intermediate 4-A to obtain an intermediate 5-A; carrying out coupling reaction on the intermediate 5-A and a compound shown as a formula (E) to obtain a compound shown as a formula (I);
the synthetic route of the compound shown in the formula (I) is shown as follows:
the synthesis steps of the compound shown in the formula (II) are as follows:
taking a compound shown in a formula (F) and a compound shown in a formula (G) as initial raw materials, and carrying out Suzuki coupling reaction to obtain an intermediate 1-B; reacting the intermediate 1-B with a compound shown as a formula (H) to obtain an intermediate 2-B; carrying out coupling reaction on the intermediate 2-B and a compound shown as a formula (J) to obtain an intermediate 3-B; the intermediate 3-B is subjected to coupling ring-closing reaction to obtain an intermediate 4-B; carrying out nitro reduction and ring closure reaction on the intermediate 4-B to obtain an intermediate 5-B; carrying out coupling reaction on the intermediate 5-B and a compound shown as a formula (K) to obtain a compound shown as a formula (II);
the synthetic route of the compound shown in the formula (II) is shown as follows:
wherein X is halogen, preferably X is selected from bromine or chlorine.
10. An organic electroluminescent device comprising a substrate, a first electrode and a second electrode formed on the substrate, and an organic layer disposed between the first electrode and the second electrode, the organic layer comprising the fused ring compound according to any one of claims 1 to 8,
the organic layer comprises at least one of a luminescent layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole blocking layer and an electron blocking layer,
preferably, the light-emitting layer includes a host material containing the fused ring compound according to any one of claims 1 to 8 and a dopant material.
11. Use of the organic electroluminescent device of claim 10 in a lighting device or a display device.
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| CN111056988B (en) | 2021-10-15 |
| CN111056988A (en) | 2020-04-24 |
| CN110698387A (en) | 2020-01-17 |
| CN111039850B (en) | 2022-02-25 |
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