CN105418667B - A kind of derivative of silicon tetraphenyl and dibenzothiophenes and preparation method thereof - Google Patents
A kind of derivative of silicon tetraphenyl and dibenzothiophenes and preparation method thereof Download PDFInfo
- Publication number
- CN105418667B CN105418667B CN201510746362.XA CN201510746362A CN105418667B CN 105418667 B CN105418667 B CN 105418667B CN 201510746362 A CN201510746362 A CN 201510746362A CN 105418667 B CN105418667 B CN 105418667B
- Authority
- CN
- China
- Prior art keywords
- derivative
- dibenzothiophenes
- silicon
- tetraphenyl
- silicon tetraphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
Abstract
The invention discloses a kind of silicon tetraphenyl and the derivative of dibenzothiophenes, the derivative has structure as shown below：
Description
Technical field
The invention belongs to ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field, more particularly, to a kind of silicon tetraphenyl and dibenzothiophenes
Derivative and its preparation method and application.
Background technology
Organic Light Emitting Diode（OLED）It is that Deng Qingyun of Kodak in 1987 et al. uses multi-layer film structure, just first
The Display Technique of the high-quantum efficiency, high-luminous-efficiency, high brightness and the low driving voltage that work out, this breakthrough make
OLED turns into the focus of luminescent device research.Compared with traditional luminous and Display Technique, OLED has that driving voltage is low, body
The advantages that product is small, in light weight, material category is abundant, and easily realize large area preparation, wet method preparation and flexible device
Prepare.But organic electroluminescence device still has short life, the problems such as luminous efficiency is low, carried out up for us
It is further to explore.
Organic Light Emitting Diode（OLED the luminous organic material) used is divided into two kinds：A kind of is small point of dyestuff and pigment
Sub- material, another kind are conjugacy high polymer materials.The OLED of small molecule structure and macromolecule OLED respectively has in material property
An eternal lasting, but with prior art development from the point of view of, as the reliability of monitor, electrical characteristic and produce stability on from the point of view of, it is small
Molecule OLEDs maintain the leading position, and the current OLED components for putting into volume production, are to use small molecule luminous organic material entirely.
Hole-transporting type material of main part is mainly injection and the transmission balance for improving device hole, improves the luminous effect of device
Rate and life-span, as hole transmission layer, it is necessary to meet with good mobility, the spy such as heat endurance, suitable HUMO energy levels
Point.Although existing a variety of hole mobile materials newly developed are applied to electroluminescent device, high electronics can be had concurrently simultaneously and moved
The hole mobile material of shifting rate and high stability is also rare.
The content of the invention
It is an object of the invention to improve the deficiency of prior art and providing a kind of can be effectively improved the four of device efficiency
The preparation method and application of the derivative of phenyl silicon and dibenzothiophenes.
The object of the present invention is achieved like this, and a kind of derivative of silicon tetraphenyl and dibenzothiophenes, its feature is
The compound has structure as shown below：
。
A kind of preparation method of the derivative of above-mentioned silicon tetraphenyl and dibenzothiophenes, is characterized in：By with alkoxy
Dibenzothiophenes silicon tetraphenyl bromo-derivative and pyridine -4- boric acid, with 1mol：1.0 ~ 3.3mol ratio is added to reaction system
In；Add the palladium catalyst and PSQ silicon substrate co-catalysts of organic microporous polymer load of catalytic amount；Add potassium carbonate or carbon
Sour sodium and mixed solvent, 5 ~ 10h is reacted under the conditions of 50 ~ 100 DEG C, obtains the derivative of silicon tetraphenyl and dibenzothiophenes, mixed
Bonding solvent is that toluene+ethanol system or THF+ aqueous systems, syntheti c route are as follows：。
Application of the derivative of above-mentioned silicon tetraphenyl and dibenzothiophenes in new energy field.
Application of the derivative of above-mentioned silicon tetraphenyl and dibenzothiophenes in OLED fields.
The design of the present invention is the silicon tetraphenyl alkane derivatives according in OLED the characteristics of hole-transporting type material of main part
It is a kind of inertia material of main part with high energy gap, this is due to its Si atom with sp3Hydridization, being total to for intramolecular is effectively blocked
Yoke, so as to have wider energy gap and higher triplet, but the mobility ratio with carrier is relatively low, heat endurance
The shortcomings of poor.The present invention is exactly using silicon tetraphenyl as agent structure, in order to preferably adjust HOMO energy levels, in dibenzo thiophene
The alkoxy with electron donation is introduced in fen, improves the HOMO energy levels of material, improves its heat endurance and with higher
Triplet introduce the pyridine ring of strong electrophilicity due to and the periphery of molecule, electron injection/transmittability obtains
It is greatly enhanced.NPB is one of hole mobile material being widely used always, its glass transition temperature Tg=98 DEG C, Tm=290
DEG C, mobility is 5.1 × 10-4cm2/ Vs, in order to improve the heat endurance of molecule, this patent have devised with silicon tetraphenyl and
The derivative of dibenzothiophenes.
Beneficial effects of the present invention are as follows：
1. the present invention is using dibenzothiophenes of the silicon tetraphenyl group connection with cavity transmission ability and carries alkoxy
Side chain, it is possible to reduce intermolecular reunion and interaction.
2. this patent introduces strong electrophilicity and has the pyridine of electronic transmission structures on the body construction, and electron injection/
Transmittability is greatly improved.
3. the present invention has preferable heat endurance, wherein decomposition temperature is more than 426 DEG C, and glass transition temperature is more than 112
℃。
4. hole-transporting type material of main part of the present invention as OLED, with Ir（ppy）3As guest materials, device
Maximum current efficiency, power efficiency and external quantum efficiency be respectively for 85.2cd/A, 78.1Im/W, 27.2%；In high electric field（1
×106V/cm）When mobility be 2 × 10-5cm-2/ Vs, show that the derivative has electron mobility.
Compound see the table below with NPB correction datas in the present invention：
| Compound name | Molecular weight | Fusing point/DEG C | Glass transition temperature/DEG C | Hole mobility/cm-2/Vs |
| NPB | 589 | 290 | 98 | 5.1×10-4 |
| Ⅶ-1 | 656 | 300 | 112 | 3.9×10-3 |
| Ⅶ-2 | 684 | 291 | 118 | 4.0×10-3 |
| Ⅶ-3 | 712 | 310 | 125 | 4.3×10-3 |
As shown by data, hole-transporting type material of main part of the invention has excellent hole transport performance, while has electronics
Transmission characteristic, shown available for OLED.
Embodiment
The present invention is further described with reference to embodiments, it is necessary to which explanation is following embodiment only for clear
Understand the present invention, the invention is not restricted to the embodiment.
Properties of product test event and tester：
Thermogravimetric analysis is tested by Oniversal V2.4F TA Instruments types thermogravimetric analyzer, and DSC is by TA DSC
Q20 type differential scannings instrument determines.
Absorption spectrum is determined by UV-4802 type dual-beams ultraviolet-uisible spectrophotometer, fluorescence spectrum and fluorescent quantum effect
Rate is by 970CRT fluorescence spectrophotometer measurements.
The measurement of fluorescence quantum efficiency is using PBD as standard substance, and its Ф=1.0, fluorescence quantum efficiency is according to following public affairs
Formula is calculated：The integral area of Ф v=(As/Au) Ф s, wherein As, Au difference determinand and reference material emission spectrum, Ф s are
The luminous efficiency of reference material.
Japanese Shimadzu LC-10ATvp types high pressure liquid chromatograph (methanol：Acetonitrile=2：1, flow velocity 1ml/min)；Day island proper
Tianjin GC-14C, GC-17A gas chromatograph（DB-1 type pillars）；Japanese Shimadzu GCMS-2014C type mass spectrographs.
Embodiment 1, a kind of derivative of silicon tetraphenyl and dibenzothiophenes, the derivative have structure as shown below：
, the derivative has hole transporting properties, shown available for OLED；This
In embodiment, R is methyl, and the structure of the derivative is as follows：
Said derivative is prepared using following steps：
The wherein preparation of chemical compounds I：
Under argon gas protection, Isosorbide-5-Nitrae-'-dibromobiphenyl 14.87g, tetrahydrofuran 210 mL are sequentially added into there-necked flask, it is cold
But to -78 DEG C, 26.25 mL n-BuLis is added dropwise, are added dropwise, stirred 1 hour at -78 DEG C, then 7.59 g are slowly added dropwise
Dichloro base silane, insulation reaction automatic heating after 1 hour is added dropwise, reaction is overnight.Add water quenching to go out reaction, boil off molten
Agent, dichloromethane and water dissolution residual substance are added, washing separates organic layer, and organic layer adds water washing twice to neutral, organic layer
With anhydrous sodium sulfate drying, methylene chloride is steamed, for residue through column chromatography for separation, leacheate is petroleum ether：Chloroform=
35:1 (V/V), solvent is boiled off, after drying, obtain 11.0 g white crystalline powders, yield 74.2%.
The preparation of compound ii：
Dichloromethane 200ml, alchlor 32.0g, dibenzothiophenes 18.4g are added into reaction bulb and is cooled to 20 ~ 30,
After stirring 10min, start that chloroacetic chloride 17.27g is added dropwise, process temperature control is added dropwise, reaction 2h is added dropwise, is added in reaction system
10% hydrochloric acid 200ml, stirring reaction 2h, stand, separate organic phase, organic phase is washed with water to be done to neutrality, anhydrous magnesium sulfate three times
Dry, filtering, concentration filtrate obtains crude product 28.0g, crude product obtains II 20.1g, yield 75% through recrystallizing methanol to solvent is not gone out.
The preparation of compound III：
Glacial acetic acid 200ml, II product 13.4g, ammonium persulfate are added into there-necked flask, stirs 0.5h, then stirring
It is lower that concentrated sulfuric acid 0.24mol is added dropwise to system, it is added dropwise, continues to react 10h, filtering reacting liquid obtains crude product 11.0g, and ethanol is tied again
Crystalline substance obtains III 9.19g, yield 85%.
The preparation of compounds Ⅳ：
Pyridine 250ml, III 21.6g, stirring and dissolving are sequentially added into there-necked flask, iodomethane 31.24g is added dropwise, then returns
Stream reaction 3h, system cooling, filtering, concentrates filtrate, obtains product 26.3g, obtain IV 19.5g with recrystallisation from isopropanol, yield is
80%
The preparation of compound V
Under argon gas protection, IV 36.6g, tetrahydrofuran 50ml are sequentially added into there-necked flask, is cooled to -78 DEG C, is added dropwise
112.5mL n-BuLis, are added dropwise, and are stirred 1 hour at -78 DEG C, then butyl borate 62.14g is slowly added dropwise, and are added dropwise
Insulation reaction automatic heating after 1 hour, reaction is overnight.Water 200ml, concentrated hydrochloric acid 200ml, petroleum ether are added in reaction bulb
250ml, stirring 2h.Organic layer washing to neutrality, boils off solvent, by product under stirring, is poured slowly into water twice, analyses
Go out solid, filter, filter cake is dried after being eluted with petroleum ether and obtains V 25.9g.Yield is 60%.
The preparation of compound VI：
Two are added into three-necked flask（4- bromophenyls）- diphenyl silane 9.9 g, V 5.76 g, polymer support load
Pd catalyst 0.1mol%, PSQ type silicon substrate co-catalyst 0.05mol%, the g of Anhydrous potassium carbonate 2.76, the mL of tetrahydrofuran 40,
The mL of water 40, under argon gas protection, 70 DEG C of stirring reactions 2 hours, reaction finishes.Solvent is boiled off, is dissolved with dichloromethane and water
Residue, washing separate organic layer, and organic layer is washed twice to neutrality with 100mL, after boiling off solvent, toluene elution, dried
After obtain 8.0 g white powders, yield 61.2%.
The preparation of compound VII：
VI 13.15 g, the g of pyridine -4- boric acid 2.46, polymer support Pt-supported catalyst are added into there-necked flask
0.1mol%, PSQ type silicon substrate co-catalyst 0.05mol%, the g of Anhydrous potassium carbonate 2.76, the mL of tetrahydrofuran 50, water 50 mL, 70
DEG C stirring reaction 8 hours, with 100 mL dichloromethane and 100 mL water dissolution residual substances, washing, organic layer is separated, it is organic
Layer is washed with water twice to neutrality, after boiling off solvent, ethanol elution, white powder 9.47g, yield 72.2% is obtained after drying.1H
NMR (400 MHz, CDCl3) δ=8.68 (dd, J=4.5,1.6 Hz, 2H, Ar-H), 8.25-8.09 (m, 2H,
Ar-H), 7.88-7.72 (m, 7H, Ar-H), 7.71-7.63 (m, 6H, Ar-H), 7.6-7.39 (m, 12H,
Ar-H), 3.73（M, 6H, MeO-H）；LC-MS （ESI）：655 [M-H]-, elementary analysis measured value（Calculated value）/%：
C78.74（72.73）, H5.07（5.08）, N2.14（2.15）, O4.88（4.87）, S4.89（4.87）, Si4.28（4.30）.
Fusing point：300 DEG C, glass transition temperature：112 DEG C, decomposition temperature：426℃
Absorption spectrum：λmax=280nm
Fluorescence spectrum：λmax=376nm
Hole mobility：3.9×10-3 cm-2/Vs
Identification confirms that the compound of synthesis is 4-（4-{[4-（2,8- dimethoxys）Dibenzo [b, d] thienyl] phenyl two
Phenyl silicon substrate } phenyl）Pyridine.
Embodiment 2, a kind of derivative of silicon tetraphenyl and dibenzothiophenes, in the present embodiment, R is ethyl, the derivative
Structure it is as follows：
The preparation method of said derivative is as follows：
The preparation process of the reference example 1 of derivative VII -2, difference are the iodomethane of the 4th step being changed to bromoethane.
Derivative VII -2： 1H NMR (400 MHz, CDCl3) δ= 8.69 (dd, J = 4.5, 1.6 Hz, 2H, Ar-H),
8.24–8.10 (m, 2H, Ar-H), 7.89–7.73 (m, 7H, Ar-H), 7.74–7.62 (m, 6H, Ar-H),
7.62-7.40 (m, 12H, Ar-H), 3.98（m, 4H, OCH2-H）, 1.33 (m, 6H, Me-H）；LC-MS （ESI）：
683 [M-H]-, elementary analysis measured value（Calculated value）/%：C79.03（79.01）, H5.45（5.47）, N2.05（2.03）,
O4.68（4.70）, S4.69（4.70）, Si4.11（4.10）.
Fusing point：291 DEG C, glass transition temperature：118 DEG C, decomposition temperature：435℃
Absorption spectrum：λmax=282nm
Fluorescence spectrum：λmax=378nm
Hole mobility：4.0×10-3 cm-2/Vs
Identification confirms that the compound of synthesis is 4-（4-{[4-（2,8- diethoxies）Dibenzo [b, d] thienyl] phenyl two
Phenyl silicon substrate } phenyl）Pyridine.
Claims (7)
- A kind of 1. derivative of silicon tetraphenyl and dibenzothiophenes, it is characterized in that the derivative has structure as shown below：R is represented：Methyl, ethyl or propyl groupThe derivative has hole transporting properties, is shown available for OLED.
- 2. the derivative of a kind of silicon tetraphenyl according to claim 1 and dibenzothiophenes, it is characterized in that the derivative has There is structure as shown below：
- 3. the derivative of a kind of silicon tetraphenyl according to claim 1 and dibenzothiophenes, it is characterized in that the derivative has There is structure as shown below：
- 4. the derivative of a kind of silicon tetraphenyl according to claim 1 and dibenzothiophenes, it is characterized in that the derivative has There is structure as shown below：
- 5. a kind of preparation method of the derivative of silicon tetraphenyl and dibenzothiophenes described in claim 1, it is characterized in that：By band The dibenzothiophenes silicon tetraphenyl bromo-derivative of alkoxy and pyridine -4- boric acid, with 1mol：1.0~3.3mol ratio is added to In reaction system；Add the palladium catalyst and PSQ silicon substrate co-catalysts of organic microporous polymer load of catalytic amount；Add carbon Sour potassium or sodium carbonate and mixed solvent, 5~10h is reacted under the conditions of 50~100 DEG C, obtain silicon tetraphenyl and dibenzothiophenes Derivative, mixed solvent are toluene+ethanol system or THF+ aqueous systems.
- A kind of 6. application of the derivative of the silicon tetraphenyl and dibenzothiophenes described in claim 1 in new energy field.
- A kind of 7. application of the derivative of the silicon tetraphenyl and dibenzothiophenes described in claim 1 in OLED fields.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510746362.XA CN105418667B (en) | 2015-11-06 | 2015-11-06 | A kind of derivative of silicon tetraphenyl and dibenzothiophenes and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510746362.XA CN105418667B (en) | 2015-11-06 | 2015-11-06 | A kind of derivative of silicon tetraphenyl and dibenzothiophenes and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105418667A CN105418667A (en) | 2016-03-23 |
| CN105418667B true CN105418667B (en) | 2018-03-13 |
Family
ID=55497260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510746362.XA Active CN105418667B (en) | 2015-11-06 | 2015-11-06 | A kind of derivative of silicon tetraphenyl and dibenzothiophenes and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105418667B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007142083A1 (en) * | 2006-06-02 | 2007-12-13 | Idemitsu Kosan Co., Ltd. | Material for organic electroluminescence element, and organic electroluminescence element using the material |
| US8748012B2 (en) * | 2011-05-25 | 2014-06-10 | Universal Display Corporation | Host materials for OLED |
| CN102391301B (en) * | 2011-09-07 | 2014-02-05 | 武汉大学 | Phosphorescent main body material |
| JP2015117210A (en) * | 2013-12-19 | 2015-06-25 | 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． | Silane compound and organic el element |
-
2015
- 2015-11-06 CN CN201510746362.XA patent/CN105418667B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105418667A (en) | 2016-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5604505B2 (en) | Synthesis of four-coordinate platinum complexes and their application to light-emitting devices | |
| CN104844587A (en) | Conjugated compound comprising phenoxathiin structure and preparation method thereof and organic electroluminescence light emitting diode device | |
| Zhan et al. | Phenothiazine substituted phenanthroimidazole derivatives: Synthesis, photophysical properties and efficient piezochromic luminescence | |
| CN109678867A (en) | A kind of phosphorescent compound and the organic light emitting diode device using the compound | |
| CN110818675A (en) | Organic compound and application thereof | |
| CN101792376A (en) | Fluorescent conjugated compound, preparation method and application thereof | |
| CN109678875A (en) | A kind of phosphorescent compound and the organic light emitting diode device using the compound | |
| WO2023165077A1 (en) | Thermally activated delayed fluorescent material based on dipyridinophenazine acceptor, and preparation method therefor and use thereof | |
| CN113861143B (en) | Thermal-activation delayed fluorescence deep blue light material, preparation method thereof and organic electroluminescent device | |
| CN107312013A (en) | A kind of application of general formula compound and organic electroluminescent | |
| CN113416175B (en) | Compound with anthracene benzofuran as core framework and application thereof | |
| Wang et al. | Synthesis, characterization, and reactions of 6, 13-disubstituted 2, 3, 9, 10-tetrakis (trimethylsilyl) pentacene derivatives | |
| Li et al. | Novel red-emitting thieno-[3, 4-b]-pyrazine derivatives suitable for vacuum evaporation and solution method to fabricate non-doped OLEDs | |
| CN111777614B (en) | Organic electroluminescent compound and application thereof | |
| CN108623639A (en) | The pyridazine platinum complexes phosphor material and its preparation method and application of butterfly alkene modification | |
| CN110845537B (en) | Synthesis and application of aryl acridine phosphine spiro-compound | |
| CN111320615B (en) | Small molecules based on S, S-dioxo-dibenzothiophene and phenanthroimidazole and application thereof in electroluminescent device | |
| CN105367595B (en) | A kind of electroluminescent hole mobile material and preparation method thereof | |
| CN105418667B (en) | A kind of derivative of silicon tetraphenyl and dibenzothiophenes and preparation method thereof | |
| Huang et al. | Efficient orange-red thermally activated delayed fluorescence material containing a cyano group | |
| CN109438468A (en) | A kind of phosphorescence host compound and its organic electroluminescence device using the compound | |
| CN105368445B (en) | A kind of electroluminescent organic material and preparation method thereof | |
| Wang et al. | A novel heteroterfluorene for efficient blue and white OLEDs | |
| CN107337678A (en) | A kind of compound for organic electroluminescence device | |
| CN109928961B (en) | Photoelectric material containing 4-sulfosulfonyl aryl dibenzofuran and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: The Yangtze River in Shandong province Laiyang City Road 265200 No. 77 Applicant after: SHANDONG SHENGHUA NEW MATERIAL TECHNOLOGY CO.,LTD. Address before: The Yangtze River Road 265200 Shandong city in Laiyang Province Economic Development Zone No. 77 Applicant before: LAIYANG SHENGHUA TECHNOLOGICAL CO.,LTD. |
|
| COR | Change of bibliographic data | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Guo Yanyun Inventor after: Bao Bin Inventor after: Shi Yongwen Inventor after: Wang Zuopeng Inventor before: Guo Yanyun Inventor before: Wang Zuopeng Inventor before: Shi Yongwen Inventor before: Wang Jinrong Inventor before: Xie Ying Inventor before: Li Peishan Inventor before: Song Yudong |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A derivative of tetraphenyl silicon and dibenzothiophene and its preparation method Effective date of registration: 20220714 Granted publication date: 20180313 Pledgee: Rizhao bank Limited by Share Ltd. Yantai branch Pledgor: SHANDONG SHENGHUA NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2022980010517 |