CN108358888B - Sulfur-containing quaternary condensed ring unit and derivatives thereof, and preparation method and application thereof - Google Patents
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Abstract
The invention belongs to the technical field of organic photoelectricity, and discloses a sulfur-containing quaternary condensed ring unit, a derivative thereof, a preparation method and application. The sulfur-containing quaternary condensed ring unit has the following chemical structural formula:
in the formula, X is-C (R)1)2‑、‑NR1‑、‑Si(R1)2-, -O-, -S-, - (SO) O-or- (CO) O-; r1Is phenyl or C1-4 alkyl; y is H, Br or I. The invention also provides a derivative of the sulfur-containing quaternary fused ring unit. The sulfur-containing quaternary condensed ring unit and the derivative thereof can be applied to an organic light-emitting diode, have a large condensed ring structure, improve the thermal stability of molecules, and have the thermal decomposition temperature of more than 350 ℃; the energy level and the band gap of the molecules are improved, and the aggregation of the molecules is inhibited; the method has higher fluorescence quantum yield, and is beneficial to improving the electroluminescent efficiency; the conjugation is enhanced, the carrier transmission performance can be improved, and the device performance is favorably improved.
Description
Technical Field
The invention belongs to the technical field of organic photoelectricity, and particularly relates to a sulfur-containing quaternary condensed ring unit, a derivative thereof, a preparation method and application.
Background
Organic Light Emitting Diodes (OLEDs) have the advantages of active light emission, high efficiency, low voltage driving, and easy fabrication of large-area devices, and have received much attention from people. OLED related research starts in the 50 th of the 20 th century, and in 1987, Duncuoyun et al, Kodak, USA, developed an OLED device with a luminance of 1000 cd-m driven by 10V DC voltage-2This is to makeOLED research has gained an epoch-making development.
The OLED device structure includes a cathode, an anode, and intervening organic layers, which typically include an electron/hole transport layer, an emissive layer. Under the action of an electric field, electrons and holes are respectively injected from the cathode and the anode and respectively migrate in the functional layer, then excitons are formed in the luminescent layer, the excitons migrate within a certain range, and finally the excitons emit light.
The light emitting material is the most central part of the OLED, determines the device emission color, and to a large extent, device efficiency and device lifetime. The efficiency of the current luminescent materials is not high enough, and the main material problems to be solved include improvement of thermal stability, fluorescence quantum yield, singlet and triplet energy levels, carrier transport performance and the like, and inhibition of molecular aggregation. The development of high-performance light-emitting materials for new systems is therefore an important issue in the research of OLEDs.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the primary object of the present invention is to provide a sulfur-containing quaternary fused ring unit.
It is another object of the present invention to provide derivatives of the above sulfur-containing quaternary fused ring units.
The invention also aims to provide a preparation method of the sulfur-containing quaternary condensed ring unit and the derivative thereof.
The invention further aims to provide application of the sulfur-containing quaternary condensed ring unit and the derivative thereof in an organic light-emitting diode.
The purpose of the invention is realized by the following scheme:
a sulfur-containing quaternary fused ring unit, the chemical structural formula of which is shown as follows:
in the formula, X is-C (R)1)2-、-NR1-、-Si(R1)2-, -O-, -S-, - (SO) O-or- (CO) O-; r1Is phenyl or C1-4 alkyl; y is H, Br or I.
The chemical structural formula of the derivative of the sulfur-containing quaternary condensed ring unit is shown as follows:
in the formula, X is-C (R)1)2-、-NR1-、-Si(R1)2-, -O-, -S-, - (SO) O-or- (CO) O-;
R1is phenyl or C1-4 alkyl;
Ar1、Ar2the same or different are each a C6-60 aromatic hydrocarbon group or a C3-60 aromatic heterocyclic group.
Ar is1、Ar2The same or different is at least one of the following chemical structures or derivatives of the following structures respectively:
the invention also provides a preparation method of the sulfur-containing quaternary condensed ring unit, which comprises the following steps:
(1) coupling bromo-or iodonaphthalene derivatives with thiol group-containing benzene derivatives under alkaline conditions to obtain ring-closing intermediate products;
(2) and (3) forming carbenium ions to realize closed loop by the ring closing intermediate under an acidic condition, so as to obtain the sulfur-containing quaternary condensed ring unit.
The acidic environment may be acetic acid, hydrochloric acid, trifluoromethanesulfonic acid, sulfuric acid, and the like.
The invention also provides a preparation method of the derivative of the sulfur-containing quaternary condensed ring unit, which comprises the following steps: bromine or iodine substitution is carried out on the sulfur-containing quaternary condensed ring unit, and then the sulfur-containing quaternary condensed ring unit and secondary aromatic amine are subjected to Ullmann coupling, Buchwald-Hartwig coupling and other reactions to realize C-N coupling, so that the sulfur-containing quaternary condensed ring unit derivative is obtained.
In the preparation method, the C-N coupling is carried out under the conditions of a catalyst, a ligand and alkalinity.
The catalyst can be palladium acetate, tris (dibenzylideneacetone) dipalladium, copper powder or cuprous iodide.
The ligand is tri-tert-butylphosphine or 1,1 '-binaphthyl-2, 2' -bis (diphenylphosphine).
The alkali is sodium tert-butoxide or potassium hydroxide.
The C-N coupling is carried out in a solvent, and the reaction solvent can be toluene, xylene and the like.
The sulfur-containing quaternary condensed ring unit and the derivative thereof can be applied to an organic light-emitting diode and used for preparing an organic light-emitting diode light-emitting layer, and the sulfur-containing quaternary condensed ring unit and/or the derivative thereof are subjected to film formation by a vacuum evaporation method to obtain the organic light-emitting diode light-emitting layer.
The invention relates to a method for preparing a sulfur-containing quaternary condensed ring unit derivative, which comprises the steps of coupling naphthalene rings and sulfur-containing benzene derivatives, then closing the rings to obtain a sulfur-containing quaternary condensed ring unit, and then coupling C-N to obtain the sulfur-containing quaternary condensed ring unit derivative. The fused ring structure of the sulfur-containing quaternary condensed ring unit is beneficial to improving the fluorescence quantum yield, the carrier mobility and the thermal stability of the polymer. The sulfur-containing quaternary condensed ring unit and the derivative thereof can be used as an organic light-emitting material to prepare an organic light-emitting diode by an evaporation method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the sulfur-containing quaternary condensed ring unit and the derivative thereof enlarge the molecular condensed ring structure through ring closing reaction, have stronger molecular rigidity, and are beneficial to improving the thermal stability of the molecules, and the thermal decomposition temperature is higher than 350 ℃.
(2) The sulfur-containing quaternary condensed ring units and the derivatives thereof have certain space distortion structures, are favorable for improving the energy level and band gap of molecules, and are favorable for inhibiting molecular aggregation.
(3) The sulfur-containing quaternary condensed ring unit and the derivative thereof have high fluorescence quantum yield and are beneficial to improving the electroluminescent efficiency.
(4) The invention provides a simple and efficient synthesis method of a sulfur-containing quaternary condensed ring unit and a derivative thereof, and the sulfur-containing quaternary condensed ring unit and the derivative thereof have good site selectivity and can obtain derivatives connected at multiple sites.
(5) The sulfur-containing quaternary condensed ring unit and the derivative thereof have large condensed ring structures, the conjugation is enhanced, the carrier transmission performance can be improved, and the device performance is favorably improved.
Drawings
FIG. 1 is a thermogravimetric plot of compound M5 of the present invention.
FIG. 2 shows photoluminescence spectra of a compound M6 of the present invention in a thin film state.
FIG. 3 is an electroluminescence spectrum of a compound M7 of the present invention, and the device structure is ITO/MeO-TPD: F4-TCNQ (4%)/NPB/ADN: M7 (5%)/Bebq 2/LiF/Al.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are commercially available.
Example 1: preparation of Compound M1
(1) Preparation of Compound 1
Under nitrogen, 1-iodo-naphthalene (2.54g, 10mmol), methyl thiosalicylate (1.68g, 10mmol), sodium tert-butoxide (4.81g, 50mmol), tris (dibenzylideneacetone) dipalladium (458mg, 0.5mmol), bis (2-diphenylphosphinophenyl) ether (269mg, 0.5mmol) and 90mL of toluene were added to a 150mL two-necked flask, and the reaction was heated to 80 ℃ and stirred for 12 hours. After the reaction was complete, the product was extracted with dichloromethane, the organic phase was washed with saturated aqueous sodium chloride solution, the solvent was evaporated under reduced pressure and the crude product was purified with petroleum ether: dichloromethane ═ 4: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, 2.65g of white solid is obtained, and the yield is 90%.1HNMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(2) Preparation of Compound 2
Under the protection of nitrogen gasAdding the compound 1(2.94g, 10mmol) and 120mL of anhydrous tetrahydrofuran into a 300mL two-mouth bottle, cooling to-78 ℃, dropwise adding a tetrahydrofuran solution of methyl magnesium bromide (30mL, 30mmol), and slowly raising the temperature to room temperature for reacting for 8 hours after dropwise adding. After the reaction, slowly adding a small amount of water to quench the reaction, extracting the product with dichloromethane, washing the organic phase with saturated aqueous sodium chloride solution, evaporating the solvent under reduced pressure, and reacting the crude product with petroleum ether: ethyl acetate 10: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, and yellow solid 2.24g is obtained, and the yield is 76%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(3) Preparation of Compound M1
Under a nitrogen atmosphere, compound 2(2.94g, 10mmol) and 80mL of acetic acid were added to a 150mL two-necked flask, heated to reflux, 5mL of hydrochloric acid was added, and the reaction was continued under reflux for 8 hours. After the reaction, the product was extracted with dichloromethane, the organic phase was washed with saturated aqueous sodium chloride solution, the solvent was distilled off under reduced pressure, and the crude product was purified by column chromatography using petroleum ether as eluent to obtain 2.21g of white solid with a yield of 80%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
The chemical reaction equations for synthesizing the compounds 1-2 and M1 are shown below:
example 2: preparation of Compound M2
Under the protection of nitrogen, compound M1(2.76g, 10mmol) and 90mL of chloroform were added to a 150mL two-necked flask, and N-bromosuccinimide was added to the flask in three portions under the exclusion of light, and the mixture was reacted at room temperature for 12 hours. After the reaction, the reaction was quenched with a suitable amount of sodium bisulfite, the product was extracted with dichloromethane, the organic phase was washed with saturated aqueous sodium chloride solution, the solvent was evaporated under reduced pressure, and the crude product was purified by column chromatography using petroleum ether as eluent to obtain 3.34g of a white solid with a yield of 77%.1H NMR、13C NMR, MS and elemental analysis results showed the obtained compoundIs a target product. The chemical reaction equation is as follows:
example 3: preparation of Compound M3
The chemical reaction equation is as follows:
(1) preparation of Compound 3
Under nitrogen, 1-bromo-4-iodo-naphthalene (3.33g, 10mmol), 4-bromo-1, 2-benzenedithiol (2.21g, 10mmol), sodium tert-butoxide (4.81g, 50mmol), tris (dibenzylideneacetone) dipalladium (458mg, 0.5mmol), bis (2-diphenylphosphinophenyl) ether (269mg, 0.5mmol) and 90mL of toluene were added to a 150mL two-necked flask, and the mixture was heated to 50 ℃ and stirred for reaction for 8 hours. After the reaction, the product was extracted with dichloromethane, the organic phase was washed with saturated aqueous sodium chloride solution, the solvent was distilled off under reduced pressure, and the crude product was purified by column chromatography using petroleum ether as eluent to obtain 2.34g of white solid with a yield of 55%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(2) Preparation of Compound 4
Under nitrogen protection, compound 3(4.26g, 10mmol), bromoethane (2.18g, 20mmol), sodium hydroxide (4.00g, 50mmol) and 80mL of N, N-dimethylformamide were added to a 150mL two-necked flask, and the reaction was stirred at room temperature for 12 hours. After the reaction, the product was extracted with dichloromethane, the organic phase was washed with saturated aqueous sodium chloride solution 5 times until the aqueous layer was clear, the solvent was removed under reduced pressure, and the crude product was purified by column chromatography using petroleum ether as eluent to obtain 3.68g of a white solid with a yield of 81%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(3) Preparation of Compound 5
To a 300mL two-necked flask, compound 4(4.54g, 10mmol) and 150mL of a mixed solvent of tetrahydrofuran and acetic acid (v: v ═ 1:1) were addedAqueous hydrogen peroxide (5mL, 10mmol) was slowly added dropwise and the reaction stirred for 12 hours. After the reaction was complete, the product was extracted with dichloromethane, washed with saturated aqueous sodium chloride solution, the solvent was removed under reduced pressure and the crude product was purified with petroleum ether: dichloromethane ═ 6: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, 3.20g of white solid is obtained, and the yield is 68%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(4) Preparation of Compound M3
Under the protection of nitrogen, adding compound 5(4.70g, 10mmol), phosphorus pentoxide (2.84g, 20mmol) and 50mL of trifluoromethanesulfonic acid into a 150mL two-necked flask, stirring at normal temperature for 24 hours, slowly pouring the reaction solution into 200mL of ice water after the reaction is finished, and washing the filter residue with deionized water after suction filtration. The residue was transferred to a 300mL two-necked flask containing 50mL of pyridine without further purification, and after 12 hours of reflux reaction, the reaction solution was quenched by pouring into ice water, and an appropriate amount of hydrochloric acid was added. The product was extracted with dichloromethane, washed with saturated aqueous sodium chloride solution, the solvent removed under reduced pressure and the crude product purified by column chromatography using petroleum ether as eluent to give M3 as a white solid 2.33g with a yield of 55%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
Example 4: preparation of Compound M4
Under nitrogen protection, compound M2(4.34g, 10mmol), diphenylamine (3.72g, 22mmol), palladium acetate (0.11g, 0.5mmol), tri-tert-butylphosphine (0.10g, 0.5mmol), sodium tert-butoxide (2.88g, 30mmol) and 90mL of toluene were added to a 150mL two-necked flask and heated to 80 ℃ for 12 hours. After the reaction is complete, cooling, extracting the product with dichloromethane, washing the organic phase with saturated aqueous sodium chloride solution, evaporating the solvent under reduced pressure, and purifying the crude product with petroleum ether: dichloromethane ═ 6: column chromatography with eluent 1 (v: v) to obtain light yellow solid 3.24g, yield 53%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product. The chemical reaction equation is as follows:
the fluorescence quantum yield of M4 in toluene solution was found to be 0.85.
Example 5: preparation of Compound M5
The chemical reaction equation is as follows:
under nitrogen protection, compound M3(4.24g, 10mmol), diphenylamine (3.72g, 22mmol), palladium acetate (0.11g, 0.5mmol), tri-tert-butylphosphine (0.10g, 0.5mmol), sodium tert-butoxide (2.88g, 30mmol) and 90mL of toluene were added to a 150mL two-necked flask and heated to 85 ℃ for 12 hours. After the reaction is complete, cooling, extracting the product with dichloromethane, washing the organic phase with saturated aqueous sodium chloride solution, evaporating the solvent under reduced pressure, and purifying the crude product with petroleum ether: dichloromethane ═ 6: column chromatography with eluent 1 (v: v) gave 4.03g of yellow solid in 67% yield. The results of 1H NMR, 13CNMR, MS and elemental analysis showed that the obtained compound was the target product.
FIG. 1 is a thermogravimetric curve of compound M5, and it can be seen that compound M5 has a thermal decomposition temperature (5% weight loss) of more than 350 ℃ and good thermal stability.
The fluorescence quantum yield of M5 in toluene solution was found to be 0.72.
Example 6: preparation of Compound M6
Under nitrogen protection, compound M2(4.34g, 10mmol), N- [1, 1-biphenyl-4-yl ] was added to a 150mL two-necked flask]-9, 9-dimethyl-9H-fluoren-2-amine (7.95g, 22mmol), copper powder (0.03g, 0.5mmol), cuprous iodide (0.10g, 0.5mmol), sodium tert-butoxide (2.88g, 30mmol) and 90mL of toluene were heated to 85 ℃ for 12 hours. After the reaction is complete, cooling, extracting the product with dichloromethane, washing the organic phase with saturated aqueous sodium chloride solution, evaporating the solvent under reduced pressure, and purifying the crude product with petroleum ether: dichloromethane ═ 6: column chromatography with eluent 1 (v: v) to obtain light yellow green solid 6.27g, yield 63%.1H NMR、13The results of CNMR, MS and elemental analysis showed that the resulting compoundsIs a target product. The chemical reaction equation is as follows:
FIG. 2 shows a photoluminescence spectrum of the compound M6 in a thin film state, from which it is understood that the maximum emission wavelength of the compound M6 is around 430nm, and shows excellent blue light emission accompanied by shoulder emission around 450 nm.
The fluorescence quantum yield of M5 in toluene solution was found to be 0.90.
Example 7: preparation of Compound M7
Under nitrogen protection, compound M2(4.34g, 10mmol), N- (1, 1-biphenyl-4-yl) benzo [ b, d ] was added to a 150mL two-necked flask]Furan-4-amine (7.38g, 22mmol), tris (dibenzylideneacetone) dipalladium (0.46g, 0.5mmol), (2,2 '-bis (diphenylphosphino) -1, 1' -binaphthyl) (0.31g, 0.5mmol), sodium tert-butoxide (2.88g, 30mmol) and 90mL of toluene were heated to 85 ℃ for 12 hours. After the reaction is complete, cooling, extracting the product with dichloromethane, washing the organic phase with saturated aqueous sodium chloride solution, evaporating the solvent under reduced pressure, and purifying the crude product with petroleum ether: dichloromethane ═ 6: column chromatography with eluent 1 (v: v) to obtain light yellow-green solid 6.51g, yield 69%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product. The chemical reaction equation is as follows:
FIG. 2 shows a device in which the compound M7 is a light-emitting layer, ITO/MeO-TPD: F4-TCNQ (4%)/NPB/ADN: M7 (5%)/Bebq 2/LiF/Al at 12mA · cm-2The electroluminescence spectrum of compound M7 shows relatively pure blue emission with device color coordinates of (0.16 ).
The fluorescence quantum yield of M7 in toluene solution was found to be 0.88.
Example 8: preparation of organic electroluminescent device
Taking the pre-made square resistor as 20Ultrasonically cleaning omega Indium Tin Oxide (ITO) glass by using acetone, a detergent, deionized water and isopropanol in sequence, and treating for 10 minutes by using plasma; evaporation of N, N' -tetrakis (4-methoxyphenyl) -benzidine (MeO-TPD) on ITO in succession: a mixed layer of 2,3,5, 6-tetrafluoro-7, 7 ', 8, 8' -tetracyanoquinodimethane (F4-TCNQ, 4%) as a hole injection layer with a thickness of 150 nm; evaporating N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) as a hole injection layer, wherein the thickness is 20 nm; vapor deposition of 9, 10-bis (2-naphthyl) Anthracene (ADN): the compound M7(3 wt%, 5 wt%, 7 wt%, respectively) was a light-emitting layer with a thickness of 25 nm; evaporation of bis (10-hydroxybenzo [ h)]Quinoline) beryllium as an electron transport layer with the thickness of 2.5 nm; evaporating lithium fluoride as an electron injection layer with the thickness of 1 nm; the vapor-deposited aluminum layer is a cathode and has a thickness of 100 nm. Wherein the evaporation deposition rate of the organic layer is 0.1nm/S, and the evaporation deposition rate of LiF is 0.01 nm/S. The structure of the device is ITO/MeO-TPD: F4-TCNQ (4%)/NPB/ADN: M7 (3%, 5%, 7%)/Bebq2The devices with a 3%, 5% and 7% ratio of compound M7 are labeled 1,2 and 3, respectively. The results are shown in Table 1 and FIG. 3.
TABLE 1 organic electroluminescent device Properties
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (2)
1. A derivative of a sulfur-containing quaternary fused ring unit is characterized by having the following chemical structural formula:
2. use of the derivative of the sulfur-containing quaternary fused ring unit of claim 1 in an organic light emitting diode.
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