CN106431968A - Platinum complex organic light-emitting material and application thereof - Google Patents

Platinum complex organic light-emitting material and application thereof Download PDF

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Publication number
CN106431968A
CN106431968A CN201610837939.2A CN201610837939A CN106431968A CN 106431968 A CN106431968 A CN 106431968A CN 201610837939 A CN201610837939 A CN 201610837939A CN 106431968 A CN106431968 A CN 106431968A
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platinum complex
emitting material
schiff base
base ligand
prepared
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张�杰
李丹
韩得满
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Taizhou University
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Taizhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)

Abstract

The invention relates to synthesis and characteristic determination of a novel Schiff base ligand and platinum complex, and belongs to the coordination chemistry field of inorganic chemistry, wherein the phosphorescence emission can be achieved effectively. According to the novel Schiff base ligand and platinum complex light-emitting material, the maximum ultraviolet absorption wavelength of the platinum complex is 487 nm, the maximum phosphorescence emission wavelength is 618 nm, and the decomposition temperature is 295 DEG C. The novel complex is convenient to synthesize, high in thermostability and not prone to decomposition under high temperature and can be prepared through a simple instrument.

Description

A kind of luminous organic material of platinum complex and its application
Technical field
The present invention relates to luminous organic material, and in particular to a kind of Yellow light emitting material of schiff bases platinum complex.
Background technology
The research of OLEDs starts from the sixties in 20th century, and professor Pope of New York Univ USA in 1963 has found have for the first time The electro optical phenomenon of machine material monocrystalline anthracene.The Tang of U.S.'s Kodak Company in 1987 is using ultra-thin membrane technology and new device Structure has made the organic electroluminescence device that running voltage is low, luminosity is high, produces the research of electroluminescent organic material Raw fundamental change.Subsequently, in nineteen ninety, the Burroughes of univ cambridge uk's Cavendish laboratory professor and Friend professor et al. has been made polymer electroluminescent device, has opened polymerization with poly- to styrene (PPV) as luminescent material Thing membrane electro luminescent device field.1997, professor Forrest of Princeton university was found that electroluminescent phosphorescence is existing As.Professor Forrest report electroluminescent phosphorescence (Phosphorescent Organic Light-emitting Devices, PHOLEDs) restriction of the technological break-through organic electroluminescent fluorescent materials quantum efficiency less than 25%.According to quantum mechanics spin statistics Theory, the probability for forming singlet exciton and triplet excitons is respectively 25%, 75%.As spin forbidden is acted on, usual In the case of, the phosphorescent emissions of triplet state are very weak, it is difficult to measure.However, in phosphor material, due to heavy metal original in coordination compound The introducing of sub (Ir, Pt, Os, Au, Cu), improves spin and the coupling of track, shortens the life-span of phosphorescence, make original three line State is provided with the characteristic of some singletstates, enhances intersystem crossing ability, causes the triplet state that prohibits to be changed into office to ground state transition Portion allows, so that phosphorescence is smoothly launched.From principle, phosphor material can utilize all of electronics and hole-recombination energy Amount is luminous, and the internal quantum efficiency of device can reach 100%, therefore attract wide attention.
Platinum complex has attracted the research interest of photoelectricity scientist as phosphorescent light-emitting materials in recent years.As this seminar exists 《J.Mater.Chem.》A series of Schiff platinum complexes are reported, these coordination compounds have the larger substituent group of volume (such as The tert-butyl group, triphenylamine etc.), the aggregation that can be effectively reduced between platinum complex molecule or the dimeric formation of sharp state, slow down Device efficiency with the landing (roll-off) of electric current, so as to be greatly enhanced device efficiency.
OLEDs luminescent material is broadly divided into micromolecular compound and two big class of high molecular polymer.Small molecule metal combination Thing is easy to purification, luminous efficiency height, good stability, can pass through vacuum vapour deposition film forming, it is considered to be most have application prospect One class luminescent material.Schiff base ligand, can be with the unoccupied orbital of metallic compound due to the lone pair electrons that have non-bonding on hetero atom Generation complex reaction, generates stable coordination compound.Such coordination compound has good luminous efficiency and a heat stability, but at present OLEDs with these coordination compounds as luminescent material is rarely reported.
Content of the invention
1. it is an object of the invention to provide a kind of platinum complex luminescent material preparation method and application.The material can launch Huang Light, can apply in field of photovoltaic materials as luminescent material.Material prepared by the present invention has good heat stability and light Property is learned, the preparation method for being adopted is simple to operate, reaction condition is gentle.
The present invention provides a kind of platinum complex luminescent material, and its structural formula is：
2. the platinum complex luminescent material that the present invention is provided includes following synthesis step：
1) aniline and 3,5- di-tert-butyl salicylaldehyde are prepared part HL by condensation
2) by Schiff base ligand HL and K2PtCl4Platinum complex Pt2L is synthesized
3. the schiff bases platinum complex luminescent material containing the tert-butyl group that the present invention is provided, with following photophysics Matter：
1) maximal ultraviolet absorption in chloroform and fluorescence emission wavelengths are respectively 487nm and 618nm；
2) heat decomposition temperature is 295 DEG C；
3) oxidoreduction (CV) curve of material, gained starting oxygen, with saturation Ag/Ag+ electrode as reference electrode, are tested Change current potential is+0.78V, is calculated the highest occupied molecular orbital of material by empirical equation [HOMO=- (Eox+4.71)] eV (HOMO) energy level is -5.49eV, is calculated the energy level of lowest unoccupied molecular orbital (LUMO) by formula [LUMO=HOMO+Eg] For -3.12eV, wherein band gap [Eg=1240/ λ max], Ag/Ag+Electrode potential is 4.71V.
4. luminescent material of the present invention can be applied in organic photoelectric display is prepared.
5. the schiff bases platinum complex luminescent material that the present invention is obtained is a kind of yellow light material, and the heat that the material has had is steady Qualitative and photophysical property.The material can be as photoelectric material in field of display application.The preparation method reaction for being adopted Simple to operate, mild condition.
Description of the drawings
Fig. 1 is the phosphorescent emissions figure of Pt2L of the present invention.
Fig. 2 is the ultravioletvisible absorption figure of Pt2L of the present invention.
Fig. 3 is the thermogravimetric analysis figure of Pt2L of the present invention.
Fig. 4 is the cyclic voltammogram of Pt2L of the present invention.
Specific embodiment
Implement row 1
1) aniline (307mg, 3.27mmol) and 3,5- di-tert-butyl salicylaldehyde (756mg, 3.23mmol) is taken, is placed in 50ml In round-bottomed flask, the dehydrated alcohol of addition 15ml, magnetic agitation, flow back 6 hours or so under 75 degrees Celsius, cold in cold room But to there is a large amount of orange/yellow solid to separate out, reduce pressure sucking filtration.With 95% washing with alcohol 2～3 times, it is placed in drying baker and dries.Product For orange-yellow powder, weigh 0.504g, and yield is 50.3%.1HMMR(CDCl3400MHZ) δ 13.69 (s, 1H, OH), 8.64 (s, 1H, HC=N), 7.47-7.38 (m, 4H, Ar-H), 7.28 (d, J=7.5Hz, 2H, Ar-H), 7.22 (d, J=2.4Hz, 1H, Ar-H), 1.48 (s, 9H, CH3), 1.33 (s, 9H, CH3).IR：3427,3180,2860,2555,2483,2328,1614, 1575,1361,1247,1170,972,866,759.C21H27NO(309.4452)：Calcd.C 81.51, H 8.79, N 4.53；Found C 81.66, H 8.64, N4.54.
2) take dried schiff base ligand (209mg, 0.67mmol) and 50ml round-bottomed flask is placed in, add 5mlDMF Dissolving, adds dry sodium hydroxide (28mg, 0.70mmol)；While weighing K2PtCl4 (148mg, 0.36mmol), it is used in combination 3mlDMSO heating for dissolving is added in reaction flask.After reacting 24 hours under anaerobic water-less environment, found with thin layer chromatography Raw material disappears substantially, has new product to generate, stopped reaction.After device is cooled down completely, on former flask, build vacuum distillation Device, steams solvent DMF and DMSO, stops heating, after device cooling, adds solid in 30ml chloroform dissolving bottle, with a point liquid Funnel is washed 5 times or so, uses 50ml deionized water wash every time.Lower floor's organic solvent rotation after wash clean is evaporated device steaming Dry.Finally with chromatography post separation impurity and product, recrystallization is centrifuged post-drying, obtains red crystals product 105mg, yield 38.6%.1HMMR(CDCl3400MHZ) δ 8.20 (s, 2H, HC=N), 7.63 (d, J=2.5Hz, 4H, Ar-H), 7.56 (d, J= 2.4Hz, 8H, Ar-H), 7.10 (d, J=2.5Hz, 1H, Ar-H), 7.01 (d, J=2.5Hz, 1H, Ar-H), 1.26 (d, J= 18.1Hz, 36H, CH3).IR：2956,2904,2868,2079,1614,1577,1523,1458,1431,1359,1255, 1172,803,701.HRMS (MALDI-TOF, positive mode, DCTB)：M/z=811.3695 [M]+(C42H52N2O2Pt： Calcd.811.3675, Δm=2.49ppm) .C42H52N2O2Pt(811.9585)：Calcd.C 62.13, H 6.46, N 3.45；Found C 62.20, H 6.41, N 3.40.
Implement row 2
Accurately weigh 10mg schiff bases platinum complex to be dissolved in chloroform, be obtained 1.0 × 10-5M solution, accurately pipettes The above-mentioned solution of 3.0ml is added in cuvette, is then determined on FLS980 luminoscope, and exciting slit and transmite slit width are all 10nm, excitation wavelength is 487nm.The measure of ultra-violet absorption spectrum inhales instrument in Shimadzu UV-2450 UV/Vis UV, visible light Determine on device.Test is carried out in room temperature and ambient atmosphere pressure.Transmitting and absorption test collection of illustrative plates normalization result are shown in Fig. 1 and Fig. 2. As can be seen from Figure 2, uv-absorption maximum wavelength is 48nm, and maximum phosphorescent emissions wavelength is 618nm.
Implement row 3
Under nitrogen protection, the thermogravimetric analysiss (TGA) of the material are carried out using TA Instruments SDTQ600 instrument Decomposition temperature is obtained for 295 DEG C, heating rate is all 10 DEG C/min.Measurement result such as Fig. 3.
Implement row 4
Accurately weigh 10mg schiff bases platinum complex to be dissolved in chloroform, be obtained 1.0 × 10-4M solution.Accurately take 4.0ml solution is added in 10.0ml beaker, tests the cyclic voltammetry curve of the compound in AUTOLAB three-electrode system, ginseng It is saturated calomel electrode than electrode, supporting electrolyte is the tetrabutyl ammonium hexafluorophosphate of 0.1mol/l, and under room temperature, scanning speed is 50mv/s, measurement result such as Fig. 4.
Specific embodiment described in the present invention is only explanation for example to present invention spirit.The affiliated technology neck of the present invention The technical staff in domain can be made various modifications or supplement or replaced using similar mode to described specific embodiment Generation, but the spirit without departing from the present invention or surmount scope defined in appended claims.

Claims (5)

1. a kind of platinum complex Yellow light emitting material, it is characterised in that structural formula is：
2. the preparation method of platinum complex Yellow light emitting material as claimed in claim 1, it is characterised in that walk including following Suddenly：
1) aniline and 3,5- di-tert-butyl salicylaldehyde are prepared Schiff base ligand HL by condensation；
2) by Schiff base ligand HL and K2PtCl4Platinum complex Pt2L is synthesized.
3. according to a kind of preparation method of the luminous organic material of platinum complex of claim 2, it is characterised in that：Step 1) in institute The part that states is Schiff base ligand, is prepared with mol ratio 1～1.25: 1 using aniline and 3,5- di-tert-butyl salicylaldehyde.
4. a kind of luminous organic material of platinum complex according to claim 2, it is characterised in that：Step 2) described in join Compound is schiff bases platinum complex, using Schiff base ligand and K2PtCl4Prepared with mol ratio 2: 1～1.25.
5. the application of the Yellow light emitting material as described in right 1, it is characterised in that：Described luminescent material can be applicable to organic light In electric display.
CN201610837939.2A 2016-09-18 2016-09-18 Platinum complex organic light-emitting material and application thereof Pending CN106431968A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109134303A (en) * 2018-07-09 2019-01-04 台州学院 A kind of red emitting material and preparation method thereof
CN109134298A (en) * 2018-07-09 2019-01-04 台州学院 A kind of preparation and application of dimerization schiff bases platinum complex
CN109251152A (en) * 2018-07-09 2019-01-22 台州学院 A kind of preparation and application of electroluminescent organic material
CN111039824A (en) * 2019-12-26 2020-04-21 台州学院 Schiff base platinum complex Pt (II) M and preparation method thereof
CN111495429A (en) * 2020-04-14 2020-08-07 南昌大学 Preparation method of efficient composite catalyst and preparation method of silane coupling agent KH-560

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109134303A (en) * 2018-07-09 2019-01-04 台州学院 A kind of red emitting material and preparation method thereof
CN109134298A (en) * 2018-07-09 2019-01-04 台州学院 A kind of preparation and application of dimerization schiff bases platinum complex
CN109251152A (en) * 2018-07-09 2019-01-22 台州学院 A kind of preparation and application of electroluminescent organic material
CN109134298B (en) * 2018-07-09 2021-03-16 台州学院 Platinum dimer Schiff base complex and preparation method and application thereof
CN111039824A (en) * 2019-12-26 2020-04-21 台州学院 Schiff base platinum complex Pt (II) M and preparation method thereof
CN111039824B (en) * 2019-12-26 2023-06-27 台州学院 Schiff base platinum complex Pt (II) M and preparation method thereof
CN111495429A (en) * 2020-04-14 2020-08-07 南昌大学 Preparation method of efficient composite catalyst and preparation method of silane coupling agent KH-560
CN111495429B (en) * 2020-04-14 2023-11-10 南昌大学 Preparation method of efficient composite catalyst and preparation method of silane coupling agent KH-560

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