CN101619045A - Double-nuclear ring metal platinum complex near-infrared light-emitting material and application thereof - Google Patents
Double-nuclear ring metal platinum complex near-infrared light-emitting material and application thereof Download PDFInfo
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Abstract
The invention discloses a double-nuclear ring metal platinum complex near-infrared light-emitting material and an application thereof. The double-nuclear ring metal platinum complex near-infrared light-emitting material comprises a ring metal ligand forming a double-nuclear ring metal platinum complex, i.e. the first ligand which is 1-phenylisoquinoline, and an auxiliary ligand forming the double-nuclear ring metal platinum complex, i.e. the second ligand which is 5-aryl-2-sulfydryl-1,3,4-oxadiazole anion ligand. The invention improves the transmission and capture function of current carriers of the double-nuclear ring metal platinum complex and the dispersing performance of the current carriers in a polymer main material, effectively inhabits the phase separation and the concentration quenching of the ring metal platinum complex in the polymer material and improves the light-emitting efficiency of a near-infrared polymer electrophosphorescent element by the 5-aryl-2-sulfydryl-1,3,4-oxadiazole anion ligand.
Description
Technical field
The present invention relates to the luminous organic material field, be particularly related to a class with 5-aryl-2-sulfydryl-1,3, the 4-oxadiazole is that negatively charged ion assistant ligand and 1-phenyl isoquinolin quinoline are double-nuclear ring metal platinum complex near-infrared light-emitting material and their application in the near infrared polymer electroluminescent device of cyclic metal complexes.
Background technology
Along with popularizing of current network technology and digital multimedia technology, the information light source is as optical communication, optical storage and the indispensable part of photoelectric display technology of high-capacity and high-speed degree, just play the part of more and more important role, and causing numerous scientists' very big interest.
At present, mainly by taking on based on the inorganic semiconductor luminescent device of inorganic materials (as III, V compounds of group), near infrared organic semiconductor luminescent device still is in the experimental study stage to the information light source.Because inorganic semiconductor luminescent device manufacture craft is very complicated, apparatus expensive is very high to the purity requirement of material; The organic semiconductor luminescent device has that preparation is simple, cost is low, flexible, change advantages such as structure, regulatory function easily, and the application potential of therefore developing the organic semiconductor luminescent device is huge.
As organic semi-conductor core integral part, the near infrared luminous organic material mainly comprises following three major types at present: the one, and the organic RE metal complexes
[1-8], the 2nd, the organic ion dyestuff
[9-10], the 3rd, heavy metal complex
[11-13]At present their near infrareds of constructing organic/the maximum external quantum efficiency of polymer electroluminescent device is less than 1%, far below visible light organic/luminous efficiency of polymer electroluminescent device, be difficult to realize that they are in they application in the information light source.
Units such as domestic Changchun applied chemistry institute, Jilin University, South China Science ﹠ Engineering University, Zhejiang University, East China University of Science, Fudan University, Northwest University, Ji'nan University, Dalian University of Technology, Zhengzhou University have carried out the research work of near-infrared light-emitting material, and having obtained result of study preferably, the maximum emission intensity of polymer device has reached 115 nanowatts
[14]But also there is bigger gap in the performance index of device from the technical requirements of near infrared information light source.
The subject matter that organic near infrared electroluminescent material and electroluminescent device thereof exist at present is: (i) near infrared electroluminescent material kind is more single, and alternative narrow range is difficult to satisfy the needs of efficient luminous near infrared electroluminescent device; Organic near infrared electroluminescent material of (ii) having reported, easy crystallization, under high current density, luminous easy cancellation; (iii) the near infrared constructed of near infrared electroluminescent material organic/luminous efficiency, luminosity and work-ing life of polymer electroluminescent device is generally on the low side, has restricted near infrared electroluminescent material and the practical application of organic/polymer electroluminescent device in fields such as optical-fibre communications, infrared source and infrared pumping laser thereof.Therefore, exploitation near infrared organic photoelectrical material efficiently luminous, stable performance seems particularly important.
For this reason, we have invented with 5-aryl-2-sulfydryl-1,3, and the 4-oxadiazole is that negatively charged ion assistant ligand and 1-phenyl isoquinolin quinoline are the double-nuclear ring metal platinum complex near-infrared light-emitting material of cyclic metal complexes.By 5-aryl-2-sulfydryl-1,3, the effect of 4-oxadiazole negatively charged ion assistant ligand, improve the carrier transport of double-nuclear ring metal platinum complex and capture effect, and their dispersing propertys in the polymer body material, suppress Cyclometalated platinum complexes being separated and concentration quenching in polymer materials effectively, improve the luminous efficiency of near infrared electrostrictive polymer phosphorescent device.
Attached: the main reference document
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[2]Tessler?N.；Medvedev?V.；Kazes?M.；Kan?S.H.；Banin?U.，Efficient?near-infrared?polymernanocrystal?light-emitting?diodes.Science，2002，295：1506-1508.
[3]Zang?F.X.；Hong?Z.R.；Li?W.L.；Li?M.T.；Sun?X.Y.，1.4μm?Band?electroluminescence?fromorganic?light-emitting?diodes?based?on?thulium?complexes.Appl.Phys.Lett.，2004，84：2679-2681.
[4]Philip?L.；Annick?S.；Jules.；Jan?D.；Christiane?G.W.；Koen?B.；K.D.；Thin?films?of?highlyluminescent?lanthanide?complexes?covalently?linked?to?an?organic-inorganic?hybrid?material?via2-substituted?imidazo[4，5-f]-1，10-phen-anthroline?groups.Chem.Mater.，2005，17：5194-5201.
[5]Oueslati?I.；Ferreira?R.A.S.；Carlos?L.D.；
C.；Berberan-Santos?M.N.；Castro?B.D.；Vicens?J.；Pischel?U.；Calix[4]azacrowns?as?novel?molecular?scaffolds?for?the?generation?of?visibleand?near-infrared?lanthanide?luminescence.Inorg.Chem.，2006，45：2652-2660.
[6]Hinds?S.；Myrskog?S.；Levina?L.；Koleilat?G.；Yang?J.；Kelley?S.O.；Sargent?E.H.；NIR-emitting?colloidal?quantum?dots?having?26％luminescence?quantum?yield?in?buffer?solution.J.Am.Chem.Soc.，2007，129：7218-7219.
[7]Oh?J.B.；Nah?M.-K.，Kim?Y.H.；Kang?M.S.；Ka?J.-W.；Kim?H.K.；Er(III)-cored?complexesbased?on?dendritic?PtII-porphyrin?ligands：synthesis，near-IR?emission?enhancement，andphotophysical?studies.Adv.Funct.Mater.，2007，17：413-424.
[8]Li?N.S.；Zhang?H.J.；Yu?J.B.；Yu?S.Y.；Peng?C.Y.；Dang?S.；Guo?X.M.；Feng?J.；Near-infraredemission?from novel?tris(8-hydroxy?quinolinate)lanthanide(III)complexes-functionalizedmesoporous?SBA-15，Langmuir.2008，24：5500-5507.
[9]Suzuki?H.；Infrared?electroluminescence?from?an?organic?ionic?dye?containing?no?rare-earthions.Apl.Phys.Lett.，2002，80：3256-3258.
[10]Suzuki?H，；Yokoo?A.；Notomi?M.；Organic?emissive?materials?and?devices?for?photoniccommunication.Polym.Adv.Technol.，2004，15：75-80.
[11]Yi?C.；Yang?C.J.；Liu?J.；Xu?M.；Wang?J.H.；Cao?Q.Y.；Gao?X.C.；Red?to?near-infraredelectrophosphorescence?from?an?iridium?complex?coordinated?with?2-phenylpyridine?and?8-hydroxyquinoline，Inorganica?Chimica?Acta.2007，360：3493-3498.
[12]Yang?C.J.；Yi?C.；Xu?M.；Wang?J.H.；Liu?Y.Z.；Gao?X.C.；Fu?J.W.；Red?to?near-infraredelectrophosphorescence?from?a?platinum?complex?coordinated?with?8-hydroxyquinoline.Appl.Phys.Lett.，2006，89：233506.
[13]Rosenow?T.C.；Walzer?K.；Leo?K.；Near-infrared?organic?light?emitting?diodes?based?on?heavymetal?phthalocyanines.J.Appl.Phys.，2008，103：043105.
[14] Ma Dongge, Xuan Yu, the trip Chinese, money is firm, Wang Zhiyuan, near infrared organic electroluminescent materials and device and preparation of devices method.
China Patent No.: 200610017222.
Summary of the invention
The purpose of this invention is to provide a class 5-aryl-2-sulfydryl-1,3,4-oxadiazole negatively charged ion assistant ligand and double-nuclear ring metal platinum complex near-infrared light-emitting material thereof.
Another object of the present invention is to provide above-mentioned 5-aryl-2-sulfydryl-1,3, the application of 4-oxadiazole negatively charged ion assistant ligand and double-nuclear ring metal platinum complex thereof.5-aryl-2-sulfydryl-1,3,4-oxadiazole negatively charged ion assistant ligand can be widely used in the preparation double-nuclear ring metal platinum complex; Double-nuclear ring metal platinum complex can be applicable to electroluminescent device as electromechanical phosphorescent material, particularly efficient luminous near infrared polymer electroluminescent device.
5-aryl of the present invention-2-sulfydryl-1,3, the structural formula of 4-oxadiazole negatively charged ion assistant ligand is:
R is hydrogen atom, the tertiary butyl, alkoxyl group or alkyl, and the carbonatoms of described alkoxyl group or alkyl is 4-18; Be preferably 6,8,12 or 16.
With above-mentioned 5-aryl-2-sulfydryl-1,3, the 4-oxadiazole is that the double-nuclear ring metal platinum complex near-infrared light-emitting material structure of negatively charged ion assistant ligand is as follows: constitute the cyclic metal complexes of double-nuclear ring metal platinum complex, promptly first part is a 1-phenyl isoquinolin quinoline; Constitute the assistant ligand of double-nuclear ring metal platinum complex, promptly second part is 5-aryl-2-sulfydryl-1,3,4-oxadiazole anion ligand, and the structural formula of this type of double-nuclear ring metal platinum complex near-infrared light-emitting material is:
R is hydrogen atom, the tertiary butyl, alkoxyl group or alkyl, and the carbonatoms of described alkoxyl group or alkyl is 4-18; Be preferably 6,8,12 or 16.
Described 5-aryl-2-sulfydryl-1,3,4-oxadiazole negatively charged ion assistant ligand can be used as second part, is used for synthetic double-nuclear ring metal platinum complex luminescent material.
Described double-nuclear ring metal platinum complex near-infrared light-emitting material can be used to prepare the dopant material of electrostrictive polymer phosphorescent device.Dopant material and conjugation or non-conjugate high molecular material of main part constitute luminescent layer; The ratio that dopant material accounts for luminescent layer is 1%～8wt%.
Above-mentioned double-nuclear ring metal platinum complex near-infrared light-emitting material comprises following any derivative:
Double-nuclear ring metal platinum complex (piq)
2Pt
2(OXT)
2: R is a hydrogen atom;
Double-nuclear ring metal platinum complex (piq)
2Pt
2(4OXT)
2: R is the tertiary butyl;
Double-nuclear ring metal platinum complex (piq)
2Pt
2(6OOXT)
2: R is a hexyloxy;
Double-nuclear ring metal platinum complex (piq)
2Pt
2(8OOXT)
2: R is an octyloxy;
Double-nuclear ring metal platinum complex (piq)
2Pt
2(12OOXT)
2: R is a dodecyl
Double-nuclear ring metal platinum complex (piq)
2Pt
2(16OOXT)
2: R is a hexadecyl
In order to obtain 5-aryl-2-sulfydryl-1,3,4-oxadiazole negatively charged ion assistant ligand and double-nuclear ring metal platinum complex thereof, concrete preparation method of the present invention is as follows:
5-aryl-2-sulfydryl-1,3,4-oxadiazole negatively charged ion assistant ligand synthetic: aryl hydrazide under the effect of alkali, with the dithiocarbonic anhydride reaction, synthetic 5-aryl-2-sulfydryl-1,3, the 4-oxadiazole of obtaining.
Synthesizing of double-nuclear ring metal platinum complex: 1-phenyl isoquinolin quinoline and potassium chloroplatinite generation chlorine bridging react, and obtain the Cyclometalated platinum dimer of chlorine bridging; Cyclometalated platinum dimer and 5-aryl-2-sulfydryl-1,3 then, 4-oxadiazole assistant ligand (second part) under the effect of salt of wormwood, goes the bridging reaction, obtains double-nuclear ring metal platinum complex, obtains pure product through column chromatography for separation.
5-aryl of the present invention-2-sulfydryl-1,3,4-oxadiazole negatively charged ion assistant ligand can be widely used in the preparation double-nuclear ring metal platinum complex.2-mercaptopyridine with bibliographical information, assistant ligands such as pyrazoles negatively charged ion are compared, introduce De oxadiazole electric transmission group, can make the double-nuclear ring metal platinum complex that forms with platinum have the enhanced carrier transport and capture ability, can improve the luminescent properties of this class double-nuclear ring metal platinum complex in polymer device.
Double-nuclear ring metal platinum complex near infrared electromechanical phosphorescent material of the present invention, compare with disclosed double-nuclear ring metal platinum complex luminescent material, be characterized in: the double-nuclear ring metal platinum complex of (1) design, contain 5-aryl-2-sulfydryl-1,3,4-oxadiazole negatively charged ion assistant ligand.Molecule Zhong De oxadiazole electric transmission group helps improving the electric property of double-nuclear ring metal platinum complex; Alkyl in the molecule, alkoxyl group can improve the dissolving and the dispersing property of double-nuclear ring metal platinum complex, thereby greatly improve the luminescent properties of this class material in electroluminescent device, realize efficiently luminous; (2) She Ji double-nuclear ring metal platinum complex in polymer electroluminescent device, has been realized high efficiency near-infrared luminous.
Application of the present invention is: double-nuclear ring metal platinum complex is used to make the near infrared electroluminescent device as luminescent material, guest materials and dopant material, especially the near infrared polymer electroluminescent device.
Described polymer electroluminescent device comprises indium tin oxide target Conducting Glass layer (ITO), hole transmission layer, luminescent layer, and cathode layer.Hole transmission layer is polyvinyl carbazole (PVK) coating; Luminescent layer is guest materials (dopant material) and material of main part blend coating, and wherein guest materials is a double-nuclear ring metal platinum complex of the present invention, and its adulterated ratio is 1wt%～8wt%.Material of main part is poly-(9, the 9-dioctyl) fluorenes (PFO) and 2-(4-xenyl)-5-(the 4-tertiary butyl) phenyl-1,3, the blend of 4-oxadiazole (PBD), perhaps for gathering the blend of PVK and PBD, wherein PBD and PFO weight ratio be 30%: 70%, PBD and PVK weight ratio be 30%: 70%.Cathode layer is that barium metal and aluminium constitute.
Description of drawings
Fig. 1 is the uv-visible absorption spectra figure of OXT of the present invention in dichloromethane solution.
Fig. 2 is the uv-visible absorption spectra figure of 4OXT of the present invention in dichloromethane solution.
Fig. 3 is the uv-visible absorption spectra figure of 6OOXT of the present invention in dichloromethane solution.
Fig. 4 is the uv-visible absorption spectra figure of 8OOXT of the present invention in dichloromethane solution.
Fig. 5 is the uv-visible absorption spectra figure of 12OOXT of the present invention in dichloromethane solution.
Fig. 6 is the uv-visible absorption spectra figure of 16OOXT of the present invention in dichloromethane solution.
Fig. 7 is (piq) of the present invention
2Pt
2(OXT)
2Uv-visible absorption spectra figure in dichloromethane solution.
Fig. 8 is (piq) of the present invention
2Pt
2(4OXT)
2Uv-visible absorption spectra figure in dichloromethane solution.
Fig. 9 is (piq) of the present invention
2Pt
2(6OOXT)
2Uv-visible absorption spectra figure in dichloromethane solution.
Figure 10 is (piq) of the present invention
2Pt
2(8OOXT)
2Uv-visible absorption spectra figure in dichloromethane solution.
Figure 11 is (piq) of the present invention
2Pt
2(12OOXT)
2Uv-visible absorption spectra figure in dichloromethane solution.
Figure 12 is (piq) of the present invention
2Pt
2(16OOXT)
2Uv-visible absorption spectra figure in dichloromethane solution.
Figure 13 is (piq) of the present invention
2Pt
2(OXT)
2Fluorescence emission spectrogram in dichloromethane solution.
Figure 14 is (piq) of the present invention
2Pt
2(4OXT)
2Fluorescence emission spectrogram in dichloromethane solution.
Figure 15 is (piq) of the present invention
2Pt
2(6OOXT)
2Fluorescence emission spectrogram in dichloromethane solution.
Figure 16 is (piq) of the present invention
2Pt
2(8OOXT)
2Fluorescence emission spectrogram in dichloromethane solution.
Figure 17 is (piq) of the present invention
2Pt
2(12OOXT)
2Fluorescence emission spectrogram in dichloromethane solution.
Figure 18 is (piq) of the present invention
2Pt
2(16OOXT)
2Fluorescence emission spectrogram in dichloromethane solution.
Figure 19 is (piq) of the present invention
2Pt
2(8OOXT)
2Electroluminescent spectrum figure in the PFO-PBD device.
Figure 20 is (piq) of the present invention
2Pt
2(8OOXT)
2External quantum efficiency in the PFO-PBD device and current density graphic representation.
Figure 21 is (piq) of the present invention
2Pt
2(8OOXT)
2Voltage in the PFO-PBD device and current density graphic representation.
Figure 22 is (piq) of the present invention
2Pt
2(8OOXT)
2Voltage in the PFO-PBD device and brightness curve figure.
Figure 23 is (piq) of the present invention
2Pt
2(8OOXT)
2Electroluminescent spectrum figure in the PVK-PBD device.
Figure 24 is (piq) of the present invention
2Pt
2(8OOXT)
2Current efficiency in the PVK-PBD device and current density graphic representation.
Figure 25 is (piq) of the present invention
2Pt
2(8OOXT)
2Voltage in the PVK-PBD device and current density graphic representation.
Figure 26 is (piq) of the present invention
2Pt
2(8OOXT)
2Voltage in the PVK-PBD device and brightness curve figure.
Embodiment
The invention will be further described below by specific embodiment, but the protection domain that these specific embodiments do not limit the present invention in any way.
Synthesizing of aryl formyl hydrazine
1.1 benzoyl hydrazine
The methyl benzoate that in the 100mL there-necked flask, adds 40mL ethanol and 0.025mol, be heated to 60 ℃, stir the hydrazine hydrate that slowly drips 6.3g (0.1mol) 80% down, drip and finish, backflow 16h, TLC follows the tracks of reaction. and question response finishes, and most of solvent is removed in underpressure distillation, reaction mixture is poured in the frozen water, separate out a large amount of white solids, suction filtration, washing, and use a small amount of petroleum ether, vacuum-drying, the dehydrated alcohol recrystallization gets 2.93g white plates crystal, yield 86.1%, m.p.113～115 ℃.1H?NMR(400MHz，CDCl
3，TMS，δppm)：7.87(t，J＝7.22，1.39Hz，2H)；7.49(s，1H)；7.65(t，J＝7.39，7.32Hz，1H)；7.56(t，J＝7.78，7.24Hz，2H)。
1.2 4-hexyloxy benzoyl hydrazine
Method is with 1.1,4.92g white plates crystal, yield 83.1%, m.p.100～102 ℃.1H?NMR(400MHz，CDCl
3，TMS，δppm)：7.69(d，J＝8.48Hz，2H)；6.91(d，J＝8.52Hz，2H)；3.98(t，J＝6.48，6.56Hz，2H)；1.77(m，2H)；1.35(m，6H)；0.90(t，J＝6.80，6.88Hz，3H)。
1.3 4-octyloxy benzoyl hydrazine
Method is with 1.1,5.36g white plates crystal, yield 81.2%, m.p.90～92 ℃.1H?NMR(400MHz，CDCl
3，TMS，δppm)：7.70(d，J＝8.68Hz，2H)；7.57(s，1H)；6.91(d，J＝8.68Hz，2H)；4.21(s，2H)；3.98(t，J＝6.56，6.52Hz，2H)；1.79(m，2H)；1.43(m，9H)；0.90(t，J＝6.44，6.88Hz，3H)。
1.4 4-dodecyloxy benzoyl hydrazine
Method is with 1.1,4.66g white plates crystal, yield 58.2%, m.p.104～106 ℃.1H?NMR(400MHz，CDCl
3，TMS，δppm)：7.69(d，J＝8.00Hz，2H)；7.35(s，1H)；6.90(d，J＝8.08Hz，2H)；4.10(s，2H)；3.98(t，J＝6.16，6.28Hz，2H)；1.77(t，J＝6.72，7.08Hz，2H)；1.26(s，18H)；0.87(d，J＝6.72Hz，3H)。
1.5 4-n-Hexadecane oxygen base benzoyl hydrazine
Method is with 1.1,8.17g white plates crystal, yield 90.9%, m.p.116～118 ℃.1H?NMR(400MHz，CDCl
3，TMS，δppm)：7.69(d，J＝8.36Hz，2H)；7.32(s，1H)；6.90(d，J＝8.32Hz，2H)；4.08(s，2H)；3.98(t，J＝6.36，6.44Hz，2H)；1.77(m，2H)；1.43(d，J＝6.92Hz，2H)；1.25(s，24H)；0.87(t，J＝5.92，6.84Hz，3H)。
1.6 4-(N-carbazole hexyloxy) benzoyl hydrazine
Method is with 1.1,7.2g white plates crystal, yield 71.7%, m.p.156～158 ℃.1H?NMR(400MHz，CDCl
3，TMS，δppm)：8.12(d，J＝7.71Hz，2H)；7.71(d，J＝8.64Hz，2H)；7.47(t，J＝7.26，7.55Hz，2H)；7.42(d，J＝8.08Hz，2H)；7.25(t，J＝7.52，6.95Hz，2H)；6.85(d，J＝8.72Hz，2H)；4.34(t，J＝7.02，7.08Hz，2H)；3.92(t，J＝6.34，6.28Hz，2H)；1.93(m，2H)；1.74(m，2H)；1.46(d，J＝10.76Hz，2H)。
1.7 4-tert.-butylbenzene formyl hydrazine
Hydrazine hydrate (the 80%NH that in the 100mL there-necked flask, adds 20.6g (100mmol) 4-p t butylbenzoic acid ethyl ester and 40mL successively
2NH
2H2O), reflux under the nitrogen protection adds the back and continues reflux 10h.Cooling, reaction mixture is poured in the frozen water, separates out a large amount of white solids, suction filtration, washing and use a small amount of petroleum ether, vacuum-drying, the dehydrated alcohol recrystallization must 17.8g white plates crystal, m.p.122～125.0 ℃, yield 93.0%.1H?NMR(400MHz，CDCl
3，TMS，δppm)：7.69(d，J＝8.4Hz，2H)，7.46(d，J＝8.4Hz，2H)，4.12(s，2H)，1.33(s，9H)。
5-aryl-2-sulfydryl-1,3,4-oxadiazole synthetic
2.1 5-phenyl-2-sulfydryl-1,3,4-oxadiazole (OXT)
In the 50mL flask, add the 0.01mol benzoyl hydrazine successively, the ethanolic soln of the 10mL of 0.56g (0.01mol) KOH and the CS of 1.48g (0.02mol)
2Stirring heating backflow 4h, TLC follows the tracks of reaction, and after reaction finished, underpressure distillation went out solvent, add water solid is dissolved, dropwise splash into 10% hydrochloric acid and regulate pH 6～7, separate out a large amount of solids, filter and obtain crude product, ethyl alcohol recrystallization gets the 1.45g white solid, productive rate: 81.2%.m.p.214～216℃。1H?NMR(400MHz，CDCl
3，TMS，δppm)：7.93(d，J＝7.6Hz，2H)；7.57(d，J＝6.84Hz，1H)；7.51(t，J＝7.16，7.76Hz，2H)；13C?NMR(400MHz，CDCl3，TMS，δppm)：177.94，162.67，161.87，128.41，115.20，114.39。
Part 5-phenyl-2-sulfydryl-1,3,4-oxadiazole (OXT) is at dichloromethane solution (1 * 10
-5M) the uv-visible absorption spectra peak position in belongs to the π-π * transition of electron of part in 256nm and 295nm.
2.2 5-(4-hexyloxy phenyl)-2-sulfydryl-1,3,4-oxadiazole (6OOXT)
Method gets the 2.16g white solid, productive rate: 77.6% with 2.1.m.p.148～150℃。1H?NMR(400MHz，CDCl
3，TMS，δppm)：10.99(s，1H)；7.84(d，J＝8.8Hz，2H)；6.97(d，J＝8.8Hz，2H)；4.01(t，J＝6.56，6.52Hz，2H)；1.77(m，2H)；1.44(m，6H)；0.89(t，J＝6.81，6.84Hz，3H)；13C?NMR(400MHz，CDCl
3，TMS，δppm)：177.94，162.67，161.87，128.41，115.20，114.39，68.46，31.52，29.03，25.63，22.55，13.97。
Part 5-(4-hexyloxy phenyl)-2-sulfydryl-1,3,4-oxadiazole (6OOXT) is at dichloromethane solution (1 * 10
-5M) the uv-visible absorption spectra peak position in belongs to the π-π * transition of electron of part in 257nm and 302nm.
2.3 5-(4-octyloxyphenyl)-2-sulfydryl-1,3,4-oxadiazole (8OOXT)
Method gets the 1.86g white solid, productive rate: 60.7% with 2.1.m.p.128～130℃1H?NMR(400MHz，CDCl
3，TMS，δppm)：10.92(s，1H)；7.85(d，J＝8.76Hz，2H)；6.98(d，J＝8.80Hz，2H)；3.93(t，J＝6.00，5.68Hz，2H)；1.79(m，2H)；1.34(m，10H)；0.89(t，J＝6.20，6.92Hz，3H)；13C?NMR(400MHz，CDCl
3，TMS，δppm)：177.82，162.63，161.92，128.43，115.17，114.32，68.46，31.83，29.34，29.24，29.09，25.99，22.68，14.14。
Part 5-(4-octyloxyphenyl)-2-sulfydryl-1,3,4-oxadiazole (8OOXT) is at dichloromethane solution (1 * 10
-5M) the uv-visible absorption spectra peak position in belongs to the π-π * transition of electron of part in 257nm and 301nm.
2.4 5-(4-ten dioxy base phenyl)-2-sulfydryl-1,3,4-oxadiazole (12OOXT)
Method gets the 3.51g white solid, productive rate: 96.7% with 2.1.m.p.108～110℃。1H?NMR(400MHz，CDCl
3，TMS，δppm)：10.76(s，1H)；7.84(d，J＝8.76Hz，2H)；6.97(d，J＝8.76Hz，2H)；4.02(t，J＝6.48，6.56Hz，2H)；1.79(m，2H)；1.42(m，20H)；0.87(t，J＝6.32，7.00Hz，3H)；13C?NMR(400MHz，CDCl
3，TMS，δppm)：177.84，162.62，161.86，128.39，115.17，114.36，68.48，31.91，29.65，29.63，29.59，29.55，29.34，29.08，25.97，22.67，14.08。
Part 5-(4-ten dioxy base phenyl)-2-sulfydryl-1,3,4-oxadiazole (12OOXT) is at dichloromethane solution (1 * 10
-5M) the uv-visible absorption spectra peak position in belongs to the π-π * transition of electron of part in 256nm and 301nm.
2.5 5-(4-16 oxygen base phenyl)-2-sulfydryl-1,3,4-oxadiazole (16OOXT)
Method gets the 3.94g white solid, productive rate: 94.2% with 2.1.m.p.124～126℃1H?NMR(400MHz，CDCl
3，TMS，δppm)：7.84(d，J＝8.64Hz，2H)；6.97(d，J＝8.64Hz，2H)；4.02(t，J＝6.32，6.56Hz，2H)；1.79(m，2H)；1.42(s，26H)；0.87(t，J＝6.28，6.88Hz，3H)。13C?NMR(400MHz，CDCl
3，TMS，δppm)：162.33，115.04，114.75，68.36，31.92，29.69，29.57，29.41，29.34，29.12，25.12，25.98，22.67，14.06。
Part 5-(4-16 oxygen base phenyl)-2-sulfydryl-1,3,4-oxadiazole (16OOXT) is at dichloromethane solution (1 * 10
-5M) the uv-visible absorption spectra peak position in belongs to the π-π * transition of electron of part in 256nm and 301nm.
2.6 5-[4-(carbazole-N-hexyloxy) phenyl]-2-sulfydryl-1,3,4-oxadiazole (Cz6OOXT)
Method gets the 2.21g white solid, productive rate: 49.8% with 2.1.m.p.70～72℃。1H?NMR(400MHz，CDCl
3，TMS，δppm)：10.76(s，1H)；8.13(d，J＝7.68Hz，2H)；7.85(d，J＝8.64Hz，2H)；7.48(t，J＝7.64，7.40Hz，2H)；7.43(d，J＝8.04Hz，2H)；7.25(d，J＝7.28Hz，2H)；6.94(d，J＝8.68Hz，H)；4.36(t，J＝7.00，7.00Hz，2H)；3.97(t，J＝6.24，6.32Hz，2H)；1.94(m，2H)；1.79(m，2H)；1.30(d，J＝7.00Hz，4H)。13C?NMR(400MHz，CDCl
3，TMS，δppm)：177.89，162.45，161.80，140.45，128.39，125.67，122.88，120.44，118.84，115.12，114.45，108.67，68.13，42.94，28.97，28.91，27.06，25.92。
Part 5-[4-(carbazole-N-hexyloxy) phenyl]-2-sulfydryl-1,3,4-oxadiazole (Cz6OOXT) is at dichloromethane solution (1 * 10
-5M) the uv-visible absorption spectra peak position in belongs to the π-π * transition of electron of part in 264nm, 293nm and 346nm.
2.7 5-(4-tertiary butyl base)-2-sulfydryl-1,3,4-oxadiazole (4OXT)
Method gets the 1.94g white solid, productive rate: 82.5% with 2.1.m.p.162～164℃1H?NMR(400MHz，CDCl
3，TMS，δppm)：11.42(s，1H)；7.87(d，J＝8.52Hz，2H)；7.52(d，J＝8.48Hz，2H)；1.35(s，9H)；13C?NMR(400MHz，CDCl
3，TMS，δppm)：178.07，161.95，156.47，126.46，126.24，119.43，35.21，31.06。
Part 5-(4-tertiary butyl base)-2-sulfydryl-1,3,4-oxadiazole (4OXT) is at dichloromethane solution (1 * 10
-5M) the uv-visible absorption spectra peak position in belongs to the π-π * transition of electron of part in 296nm.
Embodiment 3
[(1-phenyl isoquinolin quinoline)-C2 ', N)]-[(1-phenyl isoquinolin quinoline)-N]-chlorine closes the synthetic of platinum (piq) Pt (Hpiq) Cl
In the 50mL there-necked flask, add 0.84g (2.0mmol) potassium chloroplatinite successively, 1.03g (5.0mmol) 1-phenyl isoquinolin quinoline, 27mL ethylene glycol monomethyl ether; 9mL water, under the nitrogen protection, 80 ℃ of reactions of constant temperature 16h; be cooled to room temperature; partial solvent is removed in underpressure distillation, adds a small amount of distilled water, has brown precipitate to generate; suction filtration; the gained solid is water and normal hexane washing successively, and vacuum-drying gets the 1.0g yellow solid, productive rate 77.6%.
Synthesizing of double-nuclear ring metal title complex
In the 50mL there-necked flask, add (piq) 5-aryl-2-sulfydryl-1 of Pt (Hpiq) Cl and 0.408mmol of 105mg (0.163mmol) successively, 3, the 4-oxadiazole adds an amount of methylene dichloride, after making it to dissolve fully, in reaction soln, drop into the salt of wormwood of 57mg (0.41mmol).Under the nitrogen protection, 60 ℃ of following stirring reaction 16h of constant temperature.Be cooled to room temperature, underpressure distillation removes and desolvates, and the gained solid carries out column chromatography for separation with methylene dichloride/normal hexane=2/1 (V/V) developping agent.Underpressure distillation removes and desolvates gained solid normal hexane recrystallization, vacuum-drying.
4.1 two [((1-phenyl isoquinolin quinoline)-C2 ', N)-(5-phenyl-2-sulfydryl-1,3,4-oxadiazole-S N3) closes platinum] (piq)
2Pt
2(OXT)
2
The 62mg red solid, productive rate: 66%.m.p.159～161℃。
1H?NMR(400MHz，CDCl3，TMS，δppm)：8.09(d，J＝8.60Hz，2H)，7.96(d，J＝8.68Hz，4H)，7.82(d，J＝6.36Hz，2H)，7.76(d，J＝7.56Hz，2H)，7.61(d，J＝5.28Hz，4H)，7.41(d，J＝6.48Hz，2H)，7.11(d，J＝7.68Hz，2H)，6.95(d，J＝8.52Hz，6H)，6.50(t，J＝7.44，7.32Hz，2H)，6.42(t，J＝7.40，7.56Hz，2H)。
13C?NMR(400MHz，CDCl3，TMS，δppm)：173.12，166.57，164.93，155.09，145.96，142.54，140.77，137.55，137.26，134.12，131.19，130.74，128.52，128.02，127.30，127.08，126.97，126.41，125.92，124.86，122.27，120.99，119.61。
Title complex (piq)
2Pt
2(OXT)
2At dichloromethane solution (1 * 10
-5M) the uv-visible absorption spectra peak position in belongs to the singlet charge transfer of the metal of the π-π * transition of electron of part, the permission of spinning to part respectively in 331nm, 411nm and 508nm
1The metal that MLCT, spin are forbidden is to the triplet state charge transfer of part
3MLCT; The emission peak of the fluorescence spectrum in dichloromethane solution is positioned at 721nm, belongs to the near infrared light zone.
4.2 two [((1-phenyl isoquinolin quinoline)-C2 ', N)-(5-(4-hexyloxy phenyl)-2-sulfydryl-1,3,4-oxadiazole-S N3) closes platinum] (piq)
2Pt
2(6OOXT)
2
The 49mg red solid, productive rate: 45%.m.p.136～138℃。
1H?NMR(400MHz，CDCl3，TMS，δppm)：1H?NMR(400MHz，CDCl3，TMS，δppm)：8.09(d，J＝8.60Hz，2H)，7.96(d，J＝8.68Hz，4H)，7.82(d，J＝6.36Hz，2H)，7.76(d，J＝7.56Hz，2H)，7.61(d，J＝5.28Hz，4H)，7.41(d，J＝6.48Hz，2H)，7.11(d，J＝7.68Hz，2H)，6.95(d，J＝8.52Hz，6H)，6.50(t，J＝7.44，7.32Hz，2H)，6.42(t，J＝7.40，7.56Hz，2H)。
13C?NMR(400MHz，CDCl3，TMS，δppm)：172.58，166.55，164.83，161.78，145.93，142.59，140.79，137.54，134.14，130.72，129.05，128.46，128.32，127.98，127.29，127.08，126.97，124.85，122.21，119.64，116.09，114.91，68.31，31.80，29.69，29.14，25.99，14.07。
Title complex (piq)
2Pt
2(6OOXT)
2At dichloromethane solution (1 * 10
-5M) the uv-visible absorption spectra peak position in belongs to the singlet charge transfer of the metal of the π-π * transition of electron of part, the permission of spinning to part respectively in 262nm, 301nm, 405nm and 507nm
1The metal that MLCT, spin are forbidden is to the triplet state charge transfer of part
3MLCT; The emission peak of the fluorescence spectrum in dichloromethane solution is positioned at 721nm, belongs to the near infrared light zone.
4.3 two [((1-phenyl isoquinolin quinoline)-C2 ', N)-(5-(4-octyloxyphenyl)-2-sulfydryl-1,3,4-oxadiazole-S N3) closes platinum] (piq)
2Pt
2(8OOXT)
2
55mg scarlet look solid, productive rate: 48%.m.p.125～127℃
1H?NMR(400MHz，CDCl3，TMS，δppm)：8.09(d，J＝8.60Hz，2H)，7.96(d，J＝8.68Hz，4H)，7.82(d，J＝6.36Hz，2H)，7.76(d，J＝7.56Hz，2H)，7.61(d，J＝5.28Hz，4H)，7.41(d，J＝6.48Hz，2H)，7.11(d，J＝7.68Hz，2H)，6.95(d，J＝8.52Hz，6H)，6.50(t，J＝7.44，7.32Hz，2H)，6.42(t，J＝7.40，7.56Hz，2H)，4.00(t，J＝6.64，6.48Hz，4H)，1.79(m，4H)，1.29(m，20H)，0.86(t，J＝4.81，6.80Hz，6H)。
13C?NMR(400MHz，CDCl3，TMS，δppm)：172.58，166.55，164.83，161.78，145.93，142.59，140.79，137.54，134.14，130.72，129.05，128.46，128.32，127.98，127.29，127.08，126.97，124.85，122.21，119.64，116.09，114.91，68.31，31.80，29.69，29.21，29.14，25.99，22.65，14.07。Ultimate analysis (Theoretical Calculation): C, 55.54% (52.83%); H, 5.130% (4.43%); N, 5.451% (5.96%); S, 4.153% (4.55%).
Title complex (piq)
2Pt
2(8OOXT)
2At dichloromethane solution (1 * 10
-5M) the uv-visible absorption spectra peak position in belongs to the singlet charge transfer of the metal of the π-π * transition of electron of part, the permission of spinning to part respectively in 259nm, 305nm, 408nm and 506nm
1The metal that MLCT, spin are forbidden is to the triplet state charge transfer of part
3MLCT; The emission peak of the fluorescence spectrum in dichloromethane solution is positioned at 717nm, belongs to the near infrared light zone.
4.4 two [((1-phenyl isoquinolin quinoline)-C2 ', N)-(5-(4-dodecyloxy phenyl)-2-sulfydryl-1,3,4-oxadiazole-S N3) closes platinum] (piq)
2Pt
2(12OOXT)
2
The 47mg dark red solid, productive rate: 38%.m.p.115～117℃。
1H?NMR(400MHz，CDCl3，TMS，δppm)：8.12(d，J＝8.64Hz，2H)，8.01(d，J＝8.54Hz，4H)，7.86(d，J＝6.29Hz，2H)，7.78(d，J＝7.57Hz，2H)，7.65(d，J＝6.48Hz，4H)，7.44(d，J＝6.48Hz，2H)，7.14(d，J＝7.73Hz，2H)，6.98(d，J＝8.80Hz，6H)，6.54(t，J＝7.29，7.30Hz，2H)，6.46(t，J＝7.31，6.93Hz，2H)，4.03(t，J＝6.45，6.45Hz，4H)，1.82(t，J＝6.44，7.02Hz，4H)，1.29(s，36H)，0.89(d，J＝6.82Hz，6H)。
13CNMR(400MHz，CDCl3，TMS，δppm)：172.57，166.56，164.84，161.78，145.92，142.59，140.79，137.55，134.14，130.72，128.46，128.33，127.97，127.29，127.08，126.98，124.85，122.21，119.64，116.09，114.90，68.31，31.92，29.65，29.63，29.59，29.56，29.37，29.34，29.14，25.99，22.68，14.09。
Title complex (piq)
2Pt
2(12OOXT)
2At dichloromethane solution (1 * 10
-5M) the uv-visible absorption spectra peak position in belongs to the singlet charge transfer of the metal of the π-π * transition of electron of part, the permission of spinning to part respectively in 306nm, 409nm and 504nm
1The metal that MLCT, spin are forbidden is to the triplet state charge transfer of part
3MLCT; The emission peak of the fluorescence spectrum in dichloromethane solution is positioned at 720nm, belongs to the near infrared light zone.
4.5 two [((1-phenyl isoquinolin quinoline)-C2 ', N)-(5-(4-n-Hexadecane oxygen base phenyl)-2-sulfydryl-1,3,4-oxadiazole-S N3) closes platinum] (piq)
2Pt
2(16OOXT)
2
The 41mg dark red solid, productive rate 31.0%.m.p.110～112℃。
1H?NMR(400MHz，CDCl3，TMS，δppm)：8.12(d，J＝8.64Hz，2H)，8.01(d，J＝8.54Hz，4H)，7.86(d，J＝6.29Hz，2H)，7.78(d，J＝7.57Hz，2H)，7.65(d，J＝6.48Hz，4H)，7.44(d，J＝6.48Hz，2H)，7.14(d，J＝7.73Hz，2H)，6.98(d，J＝8.80Hz，6H)，6.54(t，J＝7.29，7.30Hz，2H)，6.46(t，J＝7.31，6.93Hz，2H)，4.03(t，J＝6.45，6.45Hz，4H)，1.82(t，J＝6.44，7.02Hz，4H)，1.29(s，42H)，0.89(d，J＝6.82Hz，8H)。
13CNMR(400MHz，CDCl3，TMS，δppm)：172.57，166.56，164.84，161.78，145.92，142.59，140.79，137.55，134.14，130.72，128.46，128.33，127.97，127.29，127.08，126.98，124.85，122.21，119.64，116.09，114.90，68.31，31.92，29.65，29.63，29.59，29.56，29.37，29.34，29.14，25.99，22.68，14.09。
Title complex (piq)
2Pt
2(16OOXT)
2At dichloromethane solution (1 * 10
-5M) the uv-visible absorption spectra peak position in belongs to the singlet charge transfer of the metal of the π-π * transition of electron of part, the permission of spinning to part respectively in 264nm, 320nm, 408nm and 504nm
1The metal that MLCT, spin are forbidden is to the triplet state charge transfer of part
3MLCT; The emission peak of the fluorescence spectrum in dichloromethane solution is positioned at 716nm, belongs to the near infrared light zone.
4.6 two [((1-phenyl isoquinolin quinoline)-C2 ', N)-(5-(4-tert-butyl-phenyl)-2-sulfydryl-1,3,4-oxadiazole-S N3) closes platinum] (piq)
2Pt
2(4OXT)
2
Obtain 30mg look solid, productive rate 29.0%.m.p.108～110℃，1H?NMR(400MHz，CDCl3，TMS，δppm)：8.07(d，J＝8.72Hz，2H)，7.99(d，J＝8.36Hz，4H)，7.82(d，J＝6.40Hz，2H)，7.77(d，J＝6.96Hz，2H)，7.61(d，J＝5.44Hz，4H)，7.41(m，2H)，7.10(d，J＝7.56Hz，2H)，6.94(d，J＝6.48Hz，2H)，6.53(t，J＝6.56，7.60Hz，2H)，6.45(s，18H)，1.35(t，J＝4.81，6.80Hz，6H)。13C?NMR(400MHz，CDCl3，TMS，δppm)：173.12，166.57，164.93，155.09，145.96，142.54，140.77，137.55，137.26，134.12，131.19，130.74，128.52，128.02，127.30，127.08，126.97，126.41，125.92，124.86，122.27，120.99，119.61，35.09，31.14。Ultimate analysis (Theoretical Calculation): C, 51.91% (51.26%); H, 4.015% (3.66%); N, 6.055% (6.64%); S, 3.934% (5.07%).
Title complex (piq)
2Pt
2(4OOXT)
2At dichloromethane solution (1 * 10
-5M) the uv-visible absorption spectra peak position in belongs to the singlet charge transfer of the metal of the π-π * transition of electron of part, the permission of spinning to part respectively in 288nm, 401nm and 498nm
1The metal that MLCT, spin are forbidden is to the triplet state charge transfer of part
3MLCT; The emission peak of the fluorescence spectrum in dichloromethane solution is positioned at 722nm, belongs to the near infrared light zone.
Embodiment 5
The making of polymer electroluminescent device and the test of luminescent properties
The polymer electroluminescent device of double-nuclear ring metal platinum complex comprises: indium tin oxide target (ITO) conductive glass, cavitation layer, luminescent layer, cathode layer.Luminescent layer is made of material of main part and dopant material.Wherein material of main part is made up of PFO and PBD, perhaps is made up of PVK and PBD, and the mass ratio of PFO and PBD is PFO: PBD=70: 30; The mass ratio of PVK and PBD is PVK: PBD=70: 30; Dopant material (dopant) is a double-nuclear ring metal platinum complex, and the mass percent (x%) of dopant material in material of main part is 1～8%.
Structure and the layers of material of making polymer electroluminescent device are as follows:
Device 1:ITO/PEDOT (50nm)/PVK (40nm)/dopant (x%)+PFO: PBD (80nm)/Ba (4.0nm)/Al (150nm), device 2:ITO/PEDOT (50nm)/dopant (x%)+PVK: PBD (80nm)/Ba (4.0nm)/Al (150nm).
The production process of device 1 is as follows: on the ito glass of handling well, successively PVK hole transmission layer and the 80nm luminescent layer of the poly-dioxoethyl thiophene of spin coated 50nm/poly-p styrene sulfonic acid (PEDOT-PSS) (Bayer Batron P4083) hole injection layer, 40nm, evaporation 4.0nm barium (Ba) layer and 150nm aluminium (Al) layer successively then.The light-emitting area of device is 0.15cm
2
The production process of device 2 is as follows: on the ito glass of handling well, the poly-dioxoethyl thiophene of spin coated 50nm/poly-p styrene sulfonic acid (PEDOT-PSS) (Bayer Batron P4083) hole injection layer and 80nm luminescent layer successively, evaporation 4.0nm barium (Ba) layer and 150nm aluminium (Al) layer successively then.The light-emitting area of device is 0.15cm
2
(Tencor ALFA-Step500) measures the thickness of hole injection layer, hole transmission layer and luminescent layer with surface profiler.The thickness of Ba and Al and sedimentation velocity are measured with thickness/speed instrument (the STM-100 thickness/speed instrument of Sycon company), and the sedimentation velocity of Ba and Al is respectively 0.05～0.1nm/s and 1～2nm/s.All operations are all carried out in nitrogen glove box.
Electroluminescent spectrum (EL) is measured with the Instaspec4CCD grating spectrograph of Oriel company; Luminous efficiency is measured with the silicon photoelectric diode of standard; Electroluminescent efficiency is with S80 type totalizing instrument (USLabshere company) and cooperate the UDT3 digital photometer to measure; LASER Light Source is 325, the He-Cd laser apparatus (US Dmni Chrone company) of 442nm spectral line; Current-voltage (I-V) curve and luminous intensity-voltage (L-V) curve and external quantum efficiency are measured with Keithley source determinator.
With the double-nuclear ring metal platinum complex is dopant material, and PFO and PBD are the luminescent properties of the polymer electroluminescent device of material of main part
With embodiment 4 compounds (piq)
2Pt
2(8OOXT)
2Be dopant material, the mass percent of dopant material in material of main part is 2%, makes (piq)
2Pt
2(8OOXT)
2-PFO-PBD polymer electroluminescent device.The production process of device and testing method are identical with embodiment 5.
(piq)
2Pt
2(8OOXT)
2The electroluminescent spectrum of-PFO-PBD device as shown in figure 22.Current efficiency and current density curve are as shown in figure 23.Electric current-brightness-voltage response as shown in figure 24.The maximum emission wavelength of device is 712nm, and maximum luminousing brightness is 2068cd/m
2, send out near infrared light.Device is 7.58mA/cm in current density
2Current drives under, maximum external quantum efficiency is 6.4%, opening bright voltage is 9.75V, CIE coordinate (0.68,0.31).
Embodiment 7
With the double-nuclear ring metal platinum complex is dopant material, and PVK and PBD are the luminescent properties of the polymer electroluminescent device of material of main part
With embodiment 4 compounds (piq)
2Pt
2(8OOXT)
2Be dopant material, the mass percent of dopant material in material of main part is 8%, makes (piq)
2Pt
2(8OOXT)
2-PVK-PBD polymer electroluminescent device.The production process of device and testing method are identical with embodiment 5.
(piq)
2Pt
2(8OOXT)
2The electroluminescent spectrum of-PVK-PBD device as shown in figure 25.Current efficiency and current density curve are as shown in figure 26.Electric current-brightness-voltage response as shown in figure 27.The maximum emission wavelength of device is 692nm, and maximum luminousing brightness is 2302cd/m
2, send out near infrared light.Device is 63.1mA/cm in current density
2Current drives under, maximum external quantum efficiency is 1.4%, opening bright voltage is 5.75V, CIE coordinate (0.65,0.32).
Describe the present invention although combine preferred embodiment, the present invention is not limited to the foregoing description, is to be understood that claims have summarized scope of the present invention.Under the guidance of the present invention's design, those skilled in the art will realize that certain change that the various embodiments of the present invention scheme is carried out, all will be covered by the spirit and scope of claims of the present invention.
Claims (8)
1, a class 5-aryl-2-sulfydryl-1,3,4-oxadiazole negatively charged ion assistant ligand, it is characterized in that: the structural formula of described negatively charged ion assistant ligand is:
R is hydrogen atom, the tertiary butyl, alkoxyl group or alkyl, and the carbonatoms of described alkoxyl group or alkyl is 4-18.
2,5-aryl according to claim 1-2-sulfydryl-1,3,4-oxadiazole negatively charged ion assistant ligand is characterized in that: the carbonatoms of described alkoxyl group or alkyl is 6,8,12 or 16.
3, double-nuclear ring metal platinum complex near-infrared light-emitting material is characterized in that: constitute the cyclic metal complexes of double-nuclear ring metal platinum complex, promptly first part is a 1-phenyl isoquinolin quinoline; Constitute the assistant ligand of double-nuclear ring metal platinum complex, promptly second part is 5-aryl-2-sulfydryl-1,3,4-oxadiazole anion ligand, and the structural formula of this type of double-nuclear ring metal platinum complex near-infrared light-emitting material is:
R is hydrogen atom, the tertiary butyl, alkoxyl group or alkyl, and the carbonatoms of described alkoxyl group or alkyl is 4-18.
4, double-nuclear ring metal platinum complex near-infrared light-emitting material according to claim 3 is characterized in that: the carbonatoms of described alkoxyl group or alkyl is 6,8,12 or 16.
5, the described 5-aryl of claim 1-2-sulfydryl-1,3, the application of 4-oxadiazole negatively charged ion assistant ligand is characterized in that: described negatively charged ion assistant ligand is used for synthetic double-nuclear ring metal platinum complex luminescent material as second part.
6, the application of the described double-nuclear ring metal platinum complex near-infrared light-emitting material of claim 3, it is characterized in that: described double-nuclear ring metal platinum complex near-infrared light-emitting material is used to prepare the dopant material of electrostrictive polymer phosphorescent device.
7, the application of double-nuclear ring metal platinum complex near-infrared light-emitting material according to claim 6 is characterized in that: with described dopant material and conjugation or non-conjugate high molecular material of main part formation luminescent layer.
8, the application of double-nuclear ring metal platinum complex near-infrared light-emitting material according to claim 7 is characterized in that: the ratio that dopant material accounts for luminescent layer is 1%～8wt%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103342702A (en) * | 2013-07-11 | 2013-10-09 | 湘潭大学 | D-A-A type C<^>N ligand compound as well as C<^>N ring platinum complex and application thereof |
| CN103540157A (en) * | 2013-10-31 | 2014-01-29 | 湘潭大学 | Polymeric metal-complex functional dye containing 2-(2'-pyridyl)benzimidazole D-pi-A type structure and preparation method thereof |
| CN108285472A (en) * | 2018-03-06 | 2018-07-17 | 常州大学 | The synthesis and its application of Zig-Zag type double-nuclear ring metal platinum complex near-infrared light-emitting materials |
| CN109369726A (en) * | 2018-09-12 | 2019-02-22 | 常州大学 | The preparation and application of a kind of double-nuclear ring metal platinum (III) complex near-infrared light-emitting material |
| WO2023116587A1 (en) * | 2021-12-22 | 2023-06-29 | 广东阿格蕾雅光电材料有限公司 | Binuclear platinum complex luminescent material and application thereof |
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2009
- 2009-08-12 CN CN2009100440871A patent/CN101619045B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103342702A (en) * | 2013-07-11 | 2013-10-09 | 湘潭大学 | D-A-A type C<^>N ligand compound as well as C<^>N ring platinum complex and application thereof |
| CN103342702B (en) * | 2013-07-11 | 2015-12-02 | 湘潭大学 | A kind of D-A-A type C Λn ligand compound and C thereof Λn Cyclometalated platinum complexes and application |
| CN103540157A (en) * | 2013-10-31 | 2014-01-29 | 湘潭大学 | Polymeric metal-complex functional dye containing 2-(2'-pyridyl)benzimidazole D-pi-A type structure and preparation method thereof |
| CN103540157B (en) * | 2013-10-31 | 2015-06-24 | 湘潭大学 | Polymeric metal-complex functional dye containing 2-(2'-pyridyl)benzimidazole D-pi-A type structure and preparation method thereof |
| CN108285472A (en) * | 2018-03-06 | 2018-07-17 | 常州大学 | The synthesis and its application of Zig-Zag type double-nuclear ring metal platinum complex near-infrared light-emitting materials |
| CN109369726A (en) * | 2018-09-12 | 2019-02-22 | 常州大学 | The preparation and application of a kind of double-nuclear ring metal platinum (III) complex near-infrared light-emitting material |
| CN109369726B (en) * | 2018-09-12 | 2021-03-02 | 常州大学 | Preparation and application of binuclear cyclometalated platinum (III) complex near-infrared luminescent material |
| WO2023116587A1 (en) * | 2021-12-22 | 2023-06-29 | 广东阿格蕾雅光电材料有限公司 | Binuclear platinum complex luminescent material and application thereof |
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| CN101619045B (en) | 2011-09-14 |
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