CN108070004B - Pyridines anthracene derivant iridium-platinum complex and its synthesis and application - Google Patents
Pyridines anthracene derivant iridium-platinum complex and its synthesis and application Download PDFInfo
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- CN108070004B CN108070004B CN201611001142.5A CN201611001142A CN108070004B CN 108070004 B CN108070004 B CN 108070004B CN 201611001142 A CN201611001142 A CN 201611001142A CN 108070004 B CN108070004 B CN 108070004B
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Abstract
The invention discloses a kind of pyridines anthracene derivant iridium-platinum complex and its synthesis and application, the pyridines anthracene derivant iridium-platinum complex is centered on pyridine derivate platinum complex, along with anthryl group, entire molecule triplet is reduced to realize near infrared emission；And molecules align is acted on by anthryl group, realize double action of the metal to the effect and metal to metal of ligand charge transfer state to ligand charge transfer state, realize dual phosphorescent emissions, the pyridines anthracene derivant iridium-platinum complex can be used for temperature sensing and as electroluminescent material, be kind of new temperature sensing, unimolecule white light and a near-infrared light-emitting material.The present invention is improved by chemical structure to the pyridines anthracene derivant iridium-platinum complex key and preparation process, a kind of New temperature detection, unimolecule white light and near-infrared light-emitting material based on pyridines anthracene derivant iridium-platinum complex, and the preparation method simple possible in the present invention are obtained.
Description
Technical field
The invention belongs to organic photoelectrical material preparation and applicating technology fields, spread out more particularly, to a kind of pyridines anthracene
Biological iridium-platinum complex and its synthesis and application, the pyridines anthracene derivant iridium-platinum complex material are particularly suitable for use as
Temperature sensing and luminous organic material are applied to temperature sensing and illumination field.
Background technique
In the fields such as science, technology, industrial application and the various aspects of daily life, temperature is most basic most important
One of physical quantity.Traditional liquid or glass-stem thermometer and thermocouple thermometer need and testee phase in measurement process
Contact, under extreme measuring condition, the measurement method of this thermo-contact will have sizable limitation.In general, it contacts
The temperature measurement method of formula needs between testee and sensor through heat transfer to reach thermal balance.This is in measurement process
In can cause biggish error so that it is on speed of detection and precision by biggish limitation.Compared to traditional liquid temperature
Degree meter, the Novel thermometer based on substance optical sensing is with nontoxic, application method is simple, accuracy is high, observable temperature range
Greatly, it the advantages such as can digitize.Earliest optical sensing thermometer is infrared thermometer, it is made of according to black body radiation principle
, it is particularly useful in the place that medicine and thermocouple can not be contacted directly.But in terms of spatial resolution, infrared thermometer
Since its accuracy frequently relies on the property of testee, thus it is unable to reach higher standard.In recent years, people pay close attention to
In certain temperature range, certain optical characteristics of luminescent material, such as peak position, fluorescence intensity ratio, spectral line width, fluorescence
Intensity, polarization anisotropy and decay life time etc. change with the change of temperature.Therefore, we can be with
Temperature is demarcated using these thermally sensitive optical characteristics.Novel thermometer based on substance optic response has high-temperature
Resolution, quick response, it is contactless the advantages that.
From Kodak in 1987 report for the first time Organic Light Emitting Diode (Organic Light Emitting Diode,
Abbreviation OLED) since, by the material and optimised devices structure of continuous synthesizing new, the research of OLEDs achieves great dash forward
It is broken, tempting industrialization prospect is presented in next-generation flat-panel screens and lighting source.Then, nineteen ninety Britain Camb is big
Be proposed high molecule electroluminescent material and device, and organic electroluminescence device (OLED) causes in academia and business circles
Great sensation.1998, Forrest, Thompson and Ma etc. introduced OLED's for phosphorescent complexes as luminescent material
Luminescent layer, due to can simultaneously utilize substance and triplet excited state energy, make the theoretical maximum internal quantum efficiency of device by
25% is increased to 100%, advances major step in organic light emission field.When heavy metal such as Ir, Pt, Rh or Pd are introduced organic point
When in son, the Quantum geometrical phase occurred by heavy atoms effect, so that even if singlet state can also be carried out at room temperature to three
The transition of weight state simultaneously effectively emits phosphorescence.
Although luminous organic material technology achieves comparable progress, existing luminous organic material there are still it is photochromic not
The defects of stabilization, low efficiency, especially in terms of unimolecule white light and near-infrared material.Therefore, it needs to find and a kind of simply may be used
Capable and high synthetic yield unimolecule white light and near-infrared material.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, it is derivative that the purpose of the present invention is to provide a kind of pyridines anthracenes
Object iridium-platinum complex and its synthesis and application, wherein passing through the chemistry to the pyridines anthracene derivant iridium-platinum complex key
Structure and preparation process (including parameter and reaction condition etc. used by each step in preparation process) improve,
A kind of New temperature detection based on pyridines anthracene derivant iridium-platinum complex, unimolecule white light and near-infrared luminous are obtained
Material, and the present invention by the synthetic method of simple possible can pyridine synthesis class anthracene derivant iridium-platinum complex, the pyrrole
Pyridine class anthracene derivant iridium-platinum complex can be used for temperature sensing and as electroluminescent material, be kind of a new temperature sensing,
Unimolecule white light and near-infrared light-emitting material.
To achieve the above object, according to one aspect of the present invention, a kind of pyridines anthracene derivant platinum coordinationization is provided
Close object, which is characterized in that the pyridines anthracene derivant iridium-platinum complex has the structure as shown in following formula formula (I):
Wherein, the R1For any one in H, F, Cl, Br；R2、R3For H and as following formula formula (II), formula (III),
Any one in group shown in formula (IV)；
As present invention further optimization, which has such as formula (1)~formula
(28) structure shown in any one, wherein
For the formula (1), R1For H, R2、R3It is H；
For the formula (2), R1For F, R2、R3It is H；
For the formula (3), R1For Cl, R2、R3It is H；
For the formula (4), R1For Br, R2、R3It is H；
For the formula (5), R1For H, R2、R3It is the group as shown in the formula (II)；
For the formula (6), R1For F, R2、R3It is the group as shown in the formula (II)；
For the formula (7), R1For Cl, R2、R3It is the group as shown in the formula (II)；
For the formula (8), R1For Br, R2、R3It is the group as shown in the formula (II)；
For the formula (9), R1For H, R2、R3It is the group as shown in the formula (III)；
For the formula (10), R1For F, R2、R3It is the group as shown in the formula (III)；
For the formula (11), R1For Cl, R2、R3It is the group as shown in the formula (III)；
For the formula (12), R1For Br, R2、R3It is the group as shown in the formula (III)；
For the formula (13), R1For H, R2、R3It is the group as shown in the formula (IV)；
For the formula (14), R1For F, R2、R3It is the group as shown in the formula (IV)；
For the formula (15), R1For Cl, R2、R3It is the group as shown in the formula (IV)；
For the formula (16), R1For Br, R2、R3It is the group as shown in the formula (IV)；
For the formula (17), R1For H, R2For the group as shown in the formula (II), R3For shown in such as described formula (III)
Group；
For the formula (18), R1For F, R2For the group as shown in the formula (II), R3For shown in such as described formula (III)
Group；
For the formula (19), R1For Cl, R2For the group as shown in the formula (II), R3For shown in such as described formula (III)
Group；
For the formula (20), R1For Br, R2For the group as shown in the formula (II), R3For shown in such as described formula (III)
Group；
For the formula (21), R1For H, R2For the group as shown in the formula (II), R3For as shown in the formula (IV)
Group；
For the formula (22), R1For F, R2For the group as shown in the formula (II), R3For as shown in the formula (IV)
Group；
For the formula (23), R1For Cl, R2For the group as shown in the formula (II), R3For shown in such as described formula (IV)
Group；
For the formula (24), R1For Br, R2For the group as shown in the formula (II), R3For shown in such as described formula (IV)
Group；
For the formula (25), R1For H, R2For the group as shown in the formula (III), R3For shown in such as described formula (IV)
Group；
For the formula (26), R1For F, R2For the group as shown in the formula (III), R3For shown in such as described formula (IV)
Group；
For the formula (27), R1For Cl, R2For the group as shown in the formula (III), R3For shown in such as described formula (IV)
Group；
For the formula (28), R1For Br, R2For the group as shown in the formula (III), R3For shown in such as described formula (IV)
Group.
As present invention further optimization, sent out for the photoexcitation of the pyridines anthracene derivant iridium-platinum complex
Penetrate spectrum with main peak 500nm~600nm emission peak and main peak 700nm~800nm emission peak；Preferably, institute
Pyridines anthracene derivant iridium-platinum complex is stated to be entrained in polymethyl methacrylate.
As present invention further optimization, the main peak is based on the pyridines in the emission peak of 500nm~600nm
Effect of the metal to ligand charge transfer state in anthracene derivant iridium-platinum complex, transmitting of the main peak in 700nm~800nm
Peak is based on effect of the metal to metal to ligand charge transfer state in the pyridines anthracene derivant iridium-platinum complex.
As present invention further optimization, when the main peak is in its main peak intensity normalizing of the emission peak of 500nm~600nm
When change, the main peak reduces as the temperature rises in its main peak intensity of the emission peak of 700nm~800nm；Preferably, described
Main peak is to reduce as the temperature rises and linearly in its main peak intensity of the emission peak of 700nm~800nm；Preferably, described
Main peak within the temperature range of the emission peak of 700nm~800nm its main peak intensity is in 77K~298K as the temperature rises and
It is linear to reduce.
It is another aspect of this invention to provide that the present invention provides a kind of preparations of pyridines anthracene derivant iridium-platinum complex
Method, which comprises the following steps:
The preparation of (1) first raw material:
Under protective atmosphere, the first sub- reaction raw materials, the second sub- reaction raw materials, tetra-triphenylphosphine palladium are added to toluene
In solvent, and wet chemical or aqueous sodium carbonate are added into the toluene solvant, the first mixture is obtained after stirring；It connects
, which is carried out under the protective atmosphere of flowing in 90 DEG C~110 DEG C be heated at reflux processing 9 hours~
It 15 hours, then cools down, and the isolated organic layer of organic solvent is added；Then, which is purified and is recrystallized
Obtain the first solid, first solid i.e. the first raw material；
The ratio between mole of the first sub- reaction raw materials and the described second sub- reaction raw materials is no more than 1:2；Described first
Sub- reaction raw materials, the second sub- reaction raw materials are respectively provided with the structure being shown below:
The molar ratio of the tetra-triphenylphosphine palladium and the described first sub- reaction raw materials is 1:(10~100)；
First raw material has the structure being shown below:
(2) preparation of pyridines anthracene derivant:
Under protective atmosphere, first raw material that the step (1) is obtained, the second raw material, third raw material and
Tetra-triphenylphosphine palladium is added in toluene solvant, and wet chemical or aqueous sodium carbonate are added into the toluene solvant,
The second mixture is obtained after stirring；Then, by second mixture under the protective atmosphere of flowing in 90 DEG C~110 DEG C
It carries out being heated at reflux processing 9 hours~15 hours, then cool down, and the isolated organic layer of organic solvent is added；Then, by this
Organic layer is purified and is recrystallized to give the second solid, second solid, that is, pyridines anthracene derivant；
The ratio between mole of first raw material, second raw material and the third raw material three be 1:(1~
1.5): (1~1.5)；
Second raw material, the third raw material are respectively provided with the structure being shown below:
In the step (2), the molar ratio of the tetra-triphenylphosphine palladium and first raw material is 1:(10~100)；
The pyridines anthracene derivant has the structure being shown below:
(3) preparation of pyridines anthracene derivant iridium-platinum complex:
The pyridines anthracene derivant and platinum tetrachloride acid potassium that the step (2) obtains are added in acetic acid and obtained
To third mixture, it is then filled with protective gas into the reaction vessel for accommodating the third mixture and excludes oxygen；Then, exist
Reaction 48 hours~84 hours is heated at reflux at 130 DEG C~160 DEG C, then cooling obtains third solid precipitate, the third
Solid precipitate, that is, pyridines anthracene derivant iridium-platinum complex；
The ratio between mole of the pyridines anthracene derivant and the platinum tetrachloride acid potassium is not less than 1:1.
As present invention further optimization, the protective atmosphere is nitrogen or inert gas；The step (1) and institute
The organic solvent stated in step (2) is methylene chloride；
In the step (1), concentration of the first sub- reaction raw materials in first mixture is 1-20mmol/L；
In the step (2), concentration of first raw material in second mixture is 1-20mmol/L；
In the step (3), concentration of the pyridines anthracene derivant in the third mixture is 10-100mmol/
L。
Another aspect according to the invention, the present invention provides a kind of above-mentioned pyridines anthracene derivant iridium-platinum complexes to exist
Application in temperature sensing device or organic electroluminescence device；Preferably, the organic electroluminescence device is white light device
Part or near infrared light device.
Contemplated above technical scheme through the invention, compared with prior art, due to pyridines anthracene derivant platinum
The chemical structure etc. of complex improves, and it is white can to obtain the unimolecule based on pyridines anthracene derivant iridium-platinum complex
Luminescent material；These meet the pyridines anthracene derivant iridium-platinum complex of specified chemical structure (that is, having shown in formula I lead to
Formula), it is to add anthryl group centered on pyridine derivate platinum complex, it is close red to realize to reduce entire molecule triplet
Outer transmitting；And molecules align is acted on by anthryl group, realizes effect and gold of the metal to ligand charge transfer (MCLT) state
Belong to the dual work to metal to ligand charge transfer (metal-metal-to-ligand charge transfer, MMLCT) state
With realizing dual phosphorescent emissions.
Especially, at by 500-600nm wavelength when intensity normalization, the intensity at 700-800nm wavelength can be with temperature
Degree and linear change, highlighting the peculiar property of temperature sensing, (so-called normalized is that the spectrum under different temperatures is whole
It is normalized, so that the main peak intensity in each spectrum 500-600nm wave-length coverage is consistent).As it can be seen that of the invention
In pyridines anthracene derivant iridium-platinum complex material it is with good stability, can be widely applied to OLED screen curtain and show,
Especially OLED white-light illuminating and the illumination fields such as near-infrared luminous, and can be applied to temperature sensing field.
Pyridines anthracene derivant iridium-platinum complex in the present invention, is entrained in polymethyl methacrylate (PMMA),
In the emission spectrum of photoexcitation, there are emission peak and main peak of the main peak in 500-600nm or so in the close of 700-800nm or so
Infrared emission peak.Main peak is the effect for shifting (MCLT) state to ligand charge due to metal in the emission peak of 500-600nm or so,
Main peak is in the work that the near infrared emission peak of 700-800nm or so is due to metal to metal to ligand charge transfer (MMLCT) state
With.In the normalized situation of main peak intensity by 500-600nm or so, the main peak intensity of 700-800nm or so is in 77K
As temperature raising can be reduced linearly within the temperature range of~298K, this characteristic shows that such material can be used as temperature sensing material
Material；Wherein, 700-800nm or so emission peak intensity is to be shifted due to metal to metal to ligand charge with temperature linearity variation
(MMLCT) state is easier to be affected by temperature than metal to ligand charge transfer (MCLT) state.Pyridines anthracene derivant in the present invention
Iridium-platinum complex, by converting different R1、R2、R3Group, pair of these pyridines anthracene derivant iridium-platinum complex molecules
It is adjustable that peak emits peak position, therefore these pyridines anthracene derivant iridium-platinum complexes also can be used as unimolecule white light and close
Infrared lumious material.
28 kinds of compounds (i.e. with the compound of the structure as shown in 1~formula of formula 28) of the invention are used as temperature sensing
Material can be applied to hygrosensor.Also unimolecule white light and near-infrared light-emitting material be can be used as, organic electroluminescent is applied to
Electroluminescent layer material in device, the electroluminescence layer are phosphorescent guest material.It can be obtained by simple synthetic route
Material into the present invention, the material filming is good and property is stablized, and has unique temperature sense property, is that ideal temperature is visited
It measures and monitor the growth of standing timber material.High brightness and stability are shown in the devices simultaneously, are ideal unimolecule white light and near-infrared light-emitting material.
Material of the present invention has unique temperature sense property, in photoluminescence spectra, due to metal
Main peak is emitted in the light of 500-600nm or so, since metal to metal is to ligand to the effect of ligand charge transfer (MLCT) state
The effect of electric charge transfer (MMLCT) state launches main peak in 700-800nm near infrared light.When by main peak 500-600nm light
In the normalized situation of intensity, the main peak intensity of 700-800nm can be changed linearly with temperature, i.e., in the model of 77K to 298K
In enclosing, with the reduction of temperature, the linear ratio of main peak intensity is increased.This special performance can greatly simplify hygrosensor
Manufacturing process simplifies detection process when detection, is ideal temperature sensing material.The present invention can be widely applied to temperature spy
Survey device.
Unique Two peak emission of material of the invention issues ligand charge transfer (MLCT) state effect by adjusting metal
The peak position and metal to metal of light issue the peak position of light, it can be achieved that list to ligand charge transfer (MMLCT) state effect
Molecule white light emission.And the effect for shifting (MMLCT) state to ligand charge by enhancing metal to metal, so that near-infrared spoke
Enhancing is penetrated, material of the invention can be used as excellent near-infrared light-emitting material.It is aobvious that the present invention can be widely applied to OLED screen curtain
Show, especially OLED white-light illuminating and near-infrared luminous.
Detailed description of the invention
It is compound doped in polymethyl methacrylate that Fig. 1 is that embodiment 3 provides, structural formula is as shown in Equation 9
(PMMA) the room temperature ultra-violet absorption spectrum in, room temperature and low-temperature photoluminescence spectra；
Fig. 2 is the transient state spectrum longevity at the detection 502nm wavelength for the compound that embodiment 3 provides, structural formula is as shown in Equation 9
Life figure；
Fig. 3 is the transient state spectrum longevity at the detection 708nm wavelength for the compound that embodiment 3 provides, structural formula is as shown in Equation 9
Life figure；
It is compound doped in polymethyl methacrylate that Fig. 4 is that embodiment 3 provides, structural formula is as shown in Equation 9
(PMMA) photoluminescence spectra of different temperatures in；
It is compound doped in polymethyl methacrylate that Fig. 5 is that embodiment 3 provides, structural formula is as shown in Equation 9
(PMMA) curve that the intensity at spectrum medium wavelength 708nm varies with temperature.
Fig. 6 is the electroluminescent light spectrogram of the device for the compound that embodiment 7 provides, structural formula is as shown in Equation 9；
Fig. 7 is the device current ciency-luminance curve for the compound object that embodiment 7 provides, structural formula is as shown in Equation 9.
Fig. 8 is the electroluminescent light spectrogram of the device for the compound that embodiment 8 provides, structural formula is as shown in Equation 9；
Fig. 9 is the device current ciency-luminance curve for the compound object that embodiment 8 provides, structural formula is as shown in Equation 9.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Pyridines anthracene derivant iridium-platinum complex in the present invention has the general formula as shown in formula (I)；Pass through transformation
R1、R2、R3Group, structural formula can be preferably any one in 1~formula of formula 28 again.The preparation method institute of these compounds
Based on chemical principle, can be summarized as follows:
Following embodiment will be with the preparation method of the pyridines anthracene derivant iridium-platinum complex as shown in formula 1, formula 2, formula 9
For, the preparation method of pyridines anthracene derivant iridium-platinum complex during the present invention will be described in detail.
Embodiment 1
Pyridines anthracene derivant iridium-platinum complex its structural formula in the present embodiment is as shown in Equation 1, preparation method institute
The main chemical reactions of generation are as follows:
(1) Suzuki coupling reaction: under nitrogen protection by 3- bis- (4,4,5,5- tetramethyls -1,3,2- boric acid pinacol
Ester) benzene (2.5g, 7.58mmol), the bromo- 2- iodine pyridine (5.2g, 18.2mmol) of 5-, tetrakis triphenylphosphine palladium (105mg,
0.09mmol), toluene (300mL) and wet chemical (150mL 2M) are put into 1000ml three neck round bottom flask and are stirred,
Mixture is heated to 90 DEG C under stream of nitrogen gas protection and reacts 12 hours.Room temperature is naturally cooled to after completion of the reaction, and crude product is logical
It crosses and is washed using methylene chloride (400ml) and deionized water (4/300mL), isolate organic layer, filtered after being dried with magnesium sulfate,
Vacuum distillation obtains crude product, and crude product makees 1:2 solvent with n-hexane with methylene chloride and carries out silica gel column chromatography purification, then
It is recrystallized with n-hexane with methylene chloride, obtains white crystal 2.35g, [2- (the 5- bromine pyrrole of i.e. 1, the 3- of the white crystal bis-
Pyridine)]-benzene, yield: 80%.
(2) Suzuki coupling reaction: inciting somebody to action under nitrogen protection, 1,3- bis- [2- (5- bromopyridine)]-benzene (200mg,
0.512mmol), 9- anthracene boric acid (273mg, 1.23mmol), tetrakis triphenylphosphine palladium (29.6mg, 0.026mmol), toluene
(80mL) and wet chemical (40mL, 2M), puts into 250ml three neck round bottom flask and stirs, mixture is in stream of nitrogen gas
90 DEG C are heated under protection to react 12 hours.Room temperature is naturally cooled to after completion of the reaction, and crude product is by using methylene chloride
The washing of (40ml) and deionized water (4/30mL), isolates organic layer, and with filtering after magnesium sulfate drying, vacuum distillation is slightly produced
Product, crude product make 1:2 solvent with n-hexane with methylene chloride and carry out silica gel column chromatography purification, then with the same dichloromethane of n-hexane
Alkane is recrystallized, and white crystal 358mg is obtained, i.e. 1, the 3- of the white crystal bis- [5- (9- anthracene) -2- pyridine]-benzene, yield:
85%.
1H-NMR(400MHz,CDCl3): δ=9.003 (s, 1H), 8.835-8.840 (d, 2H), 8.581 (s, 1H),
8.296-8.320 (dd, 2H), 8.168-8.188 (d, 2H), 8.088-8.109 (d, 4H), 7.912-7.938 (dd, 2H),
7.728-7.781 (m, 6H), 7.492-7.532 (t, 4H), 7.426-7.451 (t, 4H)；
MALDI-TOF-MS (m/z): [M]+584.2252 are calculated, actual measurement 585.234.
(3) complexation reaction: in the single necked round bottom flask of 10ml, the acetic acid after going water process that 3ml is added (can be adopted
Water is removed with such as magnesium sulfate), add [5- (9- anthracene) -2- the pyridine]-benzene (100mg, 0.171mmol) of 1,3- bis- and platinum tetrachloride
Sour potassium (II) (67mg, 0.163mmol) is taken the method for filling nitrogen after freezing vacuumizes three times to exclude oxygen completely, is reacted
It is placed under reflux temperature and reacts 72 hours, the yellow or crocus solid product obtained after cooling after filtering, is successively spent
Each 5ml of ionized water, ethyl alcohol, ether is washed 3 times, and the solid of acquisition is finally dissolved in dichloromethane solution, is filtered out therein
Remaining unreacted platinum tetrachloride acid potassium (II), vacuum distillation solution obtain final product pale yellow powder 97.4mg, this is yellowish
Color powder has structure as shown in Equation 1, yield 70%.
1H-NMR(400MHz,CDCl3): δ=9.372-9.472 (d, 1H), 8.574 (s, 2H), 8.058-8.092 (m,
6H),7.982-8.002(d,2H),7.663-7.682(d,2H),7.608-7.630(d,4H),7.465-7.522(m,5H),
7.390-7.432(t,5H)；
MALDI-TOF-MS (m/z): 814.2356 are calculated；Actual measurement, 814.2816.
Embodiment 2
Its structural formula of pyridines anthracene derivant iridium-platinum complex is as shown in Equation 2 in the present embodiment, and preparation method is sent out
Raw main chemical reactions are as follows:
(1) Suzuki coupling reaction: under nitrogen protection by 2,2'- (5- fluoro- 1,3- benzene) two (4,4,5,5- tetramethyls-
1,3,2- boric acid pinacol ester) (1.74g, 5mmol), the bromo- 2- iodine pyridine (2.55g, 9mmol) of 5-, tetrakis triphenylphosphine palladium
(208mg, 0.18mmol), toluene (40mL) and wet chemical (20mL, 2M), put into 250ml three neck round bottom flask
Stirring, mixture are heated to 90 DEG C under stream of nitrogen gas protection and react 12 hours.Room temperature is naturally cooled to after completion of the reaction, it is thick to produce
Product are washed by using methylene chloride (40ml) and deionized water (4/30mL), isolate organic layer, with mistake after magnesium sulfate drying
Filter, vacuum distillation obtain crude product, and crude product makees 1:2 solvent with n-hexane with methylene chloride and carries out silica gel column chromatography purification,
Then it is recrystallized with n-hexane with methylene chloride, obtains white crystal 1.72g, yield: 85%.
(2) under nitrogen protection by 6,6'- (5- fluoro- 1,3- benzene) two (3- bromopyridine) (208mg, 0.512mmol), 9-
Anthracene boric acid (273mg, 1.23mmol), tetrakis triphenylphosphine palladium (29.6mg, 0.026mmol), toluene (80mL) and potassium carbonate
(40mL, 2M) puts into 250ml three neck round bottom flask and stirs, and mixture is heated to 90 DEG C of reactions under stream of nitrogen gas protection
12 hours.Room temperature is naturally cooled to after completion of the reaction, and crude product is by using methylene chloride (40ml) and deionized water (4/
It 30mL) washs, isolates organic layer, with filtering after magnesium sulfate drying, vacuum distillation obtains crude product, crude product methylene chloride
Make 1:2 solvent with n-hexane and carry out silica gel column chromatography purification, is then recrystallized, obtained bright with methylene chloride with n-hexane
Yellow crystals 262mg, yield: 85%.
1H-NMR(400MHz,CDCl3): δ=8.832-8.839 (d, 2H), 8.800 (s, 1H), 8.586 (s, 2H),
8.148-8.170(dd,2H),8.090-8.111(d,4H),8.021-8.048(dd,2H),7.9126-7.952(dd,2H),
7.704-7.727(dd,4H),7.494-7.534(t,4H),7.412-7.454(t,4H)；
MALDI-TOF-MS (m/z): [M]+It is calculated 602.6970；Actual measurement, 603.2286.
(3) complexation reaction: in the single necked round bottom flask of 10ml, the processed acetic acid of 3ml is added, adds 6,6'-
(fluoro- 1, the 3- benzene of 5-) two [3- (9- anthracene) bromopyridine] (100mg, 0.166mmol) and platinum tetrachloride acid potassium (II) (65mg,
0.157mmol), the method for filling nitrogen after freezing vacuumizes three times is taken to exclude oxygen completely, reaction is placed under reflux temperature
Reaction 72 hours, the yellow obtained after cooling or crocus product are after filtering, successively each with deionized water, ethyl alcohol, ether
5ml is washed 3 times, and the solid of acquisition is finally dissolved in dichloromethane solution, filters out unreacted four chlorination of residue therein
Potassium platinate (II), vacuum distillation solution obtain final product yellow powder 97.9mg, yield 75%.
1H-NMR(400MHz,CDCl3): δ=9.361-9.365 (d, 2H), 8.508 (s, 2H), 8.028-8.054 (dd,
2H),7.989-8.0010(d,2H),7.867-7.888(d,2H),7.513-7.534(d,4H),7.388-7.451(m,6H),
7.322-7.364(t,6H)；
MALDI-TOF-MS (m/z): [M]+It is calculated 832.2260；Actual measurement, 833.1835.
Embodiment 3
Pyridines anthracene derivant iridium-platinum complex its structural formula in the present embodiment is as shown in Equation 9, preparation method institute
The main chemical reactions of generation are as follows:
(1) Suzuki coupling reaction: inciting somebody to action under nitrogen protection, 1,3- bis- [2- (5- bromopyridine)]-benzene (200mg,
0.512mmol), [10- (1- naphthalene) 9- anthracene] boric acid (428mg, 1.23mmol), tetrakis triphenylphosphine palladium (29.6mg,
0.026mmol), toluene (80mL) and wet chemical (40mL, 2M), put into 250ml three neck round bottom flask and stir, and mix
It closes object and is heated to 90 DEG C of reactions 12 hours under stream of nitrogen gas protection.Room temperature is naturally cooled to after completion of the reaction, and crude product passes through
It is washed using methylene chloride (40ml) and deionized water (4/30mL), isolates organic layer, with being filtered after magnesium sulfate drying, depressurized
Distillation obtains crude product, and crude product makees 1:2 solvent with n-hexane with methylene chloride and carries out silica gel column chromatography purification, then with just
Hexane is recrystallized with methylene chloride, obtains white powder 343mg, yield: 80%.
1H-NMR (400MHz, CDCl3): δ=9.038 (s, 1H), 8.962-8.990 (dd, 2H), 8.309-8.328 (d,
2H),8.114-8.177(dd,6H),8.056-8.076(d,2H),7.762-7.782(d,6H),7.600-7.764(t,2H),
7.518-7.559 (t, 6H), 7.427-7.465 (t, 4H), 7.182-7.331 (m, 9H).
MALDI-APCI+MS(m/z):[M]+It is calculated 837.02；Actual measurement, 837.6.
(2) complexation reaction: in the single necked round bottom flask of 10ml, the processed acetic acid of 3ml is added, adds 1,3- bis-
{ 5- [10- (1- naphthalene) 9- anthracene] -2- pyridine }-benzene (100mg, 0.119mmol) and platinum tetrachloride acid potassium (II) (46.9mg,
0.113mmol), the method for filling nitrogen after freezing vacuumizes three times is taken to exclude oxygen completely, reaction is placed under reflux temperature
Reaction 72 hours, the yellow obtained after cooling or crocus product are after filtering, successively each with deionized water, ethyl alcohol, ether
5ml is washed 3 times, and the solid of acquisition is finally dissolved in dichloromethane solution, filters out unreacted four chlorination of residue therein
Potassium platinate (II), vacuum distillation solution obtain final product pale yellow powder 84.3mg, yield 70%.
1H-NMR (400MHz, DMSO): δ=9.135-9.241 (q, 1H), 8.511-8.624 (m, 3H), 8.065-
8.252(m,6H),7.774-7.824(m,6H),7.489-7.706(m,10H),7.224-7.433(m,11H),6.943-
7.011(q,2H)；
MALDI-TOF-MS (m/z): 1066.5449 are calculated；Actual measurement, 1066.5497.
Embodiment 4
Pyridines anthracene derivant iridium-platinum complex its structural formula in the present embodiment is as shown in Equation 10, preparation method institute
The main chemical reactions of generation are as follows:
(1) it incites somebody to action under nitrogen protection, 6,6'- (5- fluoro- 1,3- benzene) two (3- bromopyridine) (208mg, 0.512mmol),
[10- (1- naphthalene) 9- anthracene] boric acid (428mg, 1.23mmol), tetrakis triphenylphosphine palladium (29.6mg, 0.026mmol), toluene
(80mL) and wet chemical (40mL, 2M), puts into 250ml three neck round bottom flask and stirs, mixture is in stream of nitrogen gas
90 DEG C are heated under protection to react 12 hours.Room temperature is naturally cooled to after completion of the reaction, and crude product is by using methylene chloride
The washing of (40ml) and deionized water (4/30mL), isolates organic layer, and with filtering after magnesium sulfate drying, vacuum distillation is slightly produced
Product, crude product make 1:2 solvent with n-hexane with methylene chloride and carry out silica gel column chromatography purification, then with the same dichloromethane of n-hexane
Alkane is recrystallized, and brilliant white crystal 372mg, yield: 85% are obtained.
1H-NMR(400MHz,CDCl3): δ=9.108 (s, 1H), 8.971-9.022 (dd, 2H), 8.380-8.400 (d,
2H),8.267-8.305(t,2H),8.054-8.132(m,6H),7.734-7.863(m,7H),7.600-7.642(t,2H),
7.512-7.556(t,6H),7.420-7.458(t,4H),7.301-7.326(m,4H),7.191-7.250(m,3H)；
MALDI-APCI+MS(m/z):[M]+It is calculated 855.01；Actual measurement, 855.7.
(2) complexation reaction: in the single necked round bottom flask of 10ml, the processed acetic acid of 3ml is added, adds 6,6'-
(fluoro- 1, the 3- benzene of 5-) two { 3- [10- (1- naphthalene) -9- anthracene] bromopyridine } (100mg, 0.117mmol) and platinum tetrachloride acid potassium (II)
(46mg, 0.111mmol) takes the method for filling nitrogen after freezing vacuumizes three times to exclude oxygen completely, and reaction is placed in reflux
At a temperature of react 72 hours, the yellow or crocus product obtained after cooling after filtering, successively with deionized water, ethyl alcohol,
Each 5ml of ether is washed 3 times, and the solid of acquisition is finally dissolved in dichloromethane solution, and it is unreacted to filter out residue therein
Platinum tetrachloride acid potassium (II), vacuum distillation solution obtain final product yellow powder 35.8mg, yield 78%.
1H-NMR (400MHz, DMSO): δ=9.149-9.259 (dd, 1H), 8.521-8.987 (m, 4H), 8.108-
8.317(m,6H),7.665-7.848(m,7H),7.494-7.620(m,7H),7.293-7.419(m,11H),6.942-
7.037(m,2H)；
MALDI-TOF-MS (m/z): [M]+It is calculated 1083.23；Actual measurement, 1084.78.
Embodiment 5
Pyridines anthracene derivant iridium-platinum complex its structural formula in the present embodiment is as shown in Equation 13, preparation method institute
The main chemical reactions of generation are as follows:
(1) Suzuki coupling reaction: inciting somebody to action under nitrogen protection, 1,3- bis- [2- (5- bromopyridine)]-benzene (200mg,
0.512mmol), [10- (2- naphthalene) 9- anthracene] boric acid (273mg, 1.23mmol), tetrakis triphenylphosphine palladium (29.6mg,
0.026mmol), toluene (80mL) and wet chemical (40mL, 2M), put into 250ml three neck round bottom flask and stir, and mix
It closes object and is heated to 90 DEG C of reactions 12 hours under stream of nitrogen gas protection.Room temperature is naturally cooled to after completion of the reaction, and crude product passes through
It is washed using methylene chloride (40ml) and deionized water (4/30mL), isolates organic layer, with being filtered after magnesium sulfate drying, depressurized
Distillation obtains crude product, and crude product makees 1:2 solvent with n-hexane with methylene chloride and carries out silica gel column chromatography purification, then with just
Hexane is recrystallized with methylene chloride, obtains white powder 341mg, yield: 81%.
1H-NMR(400MHz,CDCl3): δ=9.078 (s, 1H), 8.937-8.947 (d, 2H), 8.356-8.380 (dd,
2H),8.114-8.177(dd,6H),8.056-8.076(d,2H),7.762-7.782(d,6H),7.600-7.764(t,2H),
7.518-7.559(t,6H),7.427-7.465(t,4H),7.182-7.331(m,9H)；
MALDI-APCI+MS(m/z):[M]+It is calculated 837.02；Actual measurement, 837.5.
(2) complexation reaction: in the single necked round bottom flask of 10ml, the processed acetic acid of 3ml is added, adds 1,3- bis-
{ 5- [10- (2- naphthalene) 9- anthracene] -2- pyridine }-benzene (100mg, 0.171mmol) and platinum tetrachloride acid potassium (II) (67mg,
0.163mmol), the method for filling nitrogen after freezing vacuumizes three times is taken to exclude oxygen completely, reaction is placed under reflux temperature
Reaction 72 hours, the yellow obtained after cooling or crocus product are after filtering, successively each with deionized water, ethyl alcohol, ether
5ml is washed 3 times, and the solid of acquisition is finally dissolved in dichloromethane solution, filters out unreacted four chlorination of residue therein
Potassium platinate (II), vacuum distillation solution obtain final product pale yellow powder 101.6mg, yield 73%.
1H-NMR (400MHz, CDCl3): δ=9.088-9.135 (t, 1H), 8.507-8.566 (m, 3H), 8.044-
8.234(m,10H),7.967-7.987(d,1H),7.716-7.738(d,4H),7.604-7.675(m,10H),7.450-
7.562(m,8H),7.348-7.411(m,1H),7.218-7.233(q,1H)；
MALDI-TOF-MS (m/z): [M]+It is calculated 1066.5449；Actual measurement, 1066.6595.
Embodiment 6
Pyridines anthracene derivant iridium-platinum complex its structural formula in the present embodiment is as shown in Equation 14, preparation method institute
The main chemical reactions of generation are as follows:
(1) it incites somebody to action under nitrogen protection, 6,6'- (5- fluoro- 1,3- benzene) two (3- bromopyridine) (208mg, 0.512mmol),
[10- (2- naphthalene) 9- anthracene] boric acid (428mg, 1.23mmol), tetrakis triphenylphosphine palladium (29.6mg, 0.026mmol), toluene
(80mL) and wet chemical (40mL, 2M), puts into 250ml three neck round bottom flask and stirs, mixture is in stream of nitrogen gas
90 DEG C are heated under protection to react 12 hours.Room temperature is naturally cooled to after completion of the reaction, and crude product is by using methylene chloride
The washing of (40ml) and deionized water (4/30mL), isolates organic layer, and with filtering after magnesium sulfate drying, vacuum distillation is slightly produced
Product, crude product make 1:2 solvent with n-hexane with methylene chloride and carry out silica gel column chromatography purification, then with the same dichloromethane of n-hexane
Alkane is recrystallized, and brilliant white crystal 337mg, yield: 77% are obtained.
1H-NMR(400MHz,CDCl3): δ=8.941 (s, 2H), 8.855-8.877 (d, 1H), 8.216-8.261 (m,
3H),8.016-8.169(m,10H),7.954-7.972(d,2H),7.786-7.808(d,7H),7.615-7.669(m,6H),
7.433-7.542(t,4H),7.369-7.407(t,4H)；
MALDI-APCI+MS(m/z):[M]+It is calculated 855.01；Actual measurement, 855.5.
(2) complexation reaction: in the single necked round bottom flask of 10ml, the processed acetic acid of 3ml is added, adds 6,6'-
(fluoro- 1, the 3- benzene of 5-) two { 3- [10- (2- naphthalene) -9- anthracene] bromopyridine } (100mg, 0.117mmol) and platinum tetrachloride acid potassium (II)
(46mg, 0.111mmol) takes the method for filling nitrogen after freezing vacuumizes three times to exclude oxygen completely, and reaction is placed in reflux
At a temperature of react 72 hours, the yellow or crocus product obtained after cooling after filtering, successively with deionized water, ethyl alcohol,
Each 5ml of ether is washed 3 times, and the solid of acquisition is finally dissolved in dichloromethane solution, and it is unreacted to filter out residue therein
Platinum tetrachloride acid potassium (II), vacuum distillation solution obtain final product yellow powder 32.6mg, yield 71%.
1H-NMR(400MHz,CDCl3): δ=9.488-9.579 (t, 2H), 8.216-8.233 (d, 2H), 7.938-
8.151(m,10H),7.746-7.785(t,4H),7.600-7.688(m,10H),7.335-7.515(m,10H)；
MALDI-TOF-MS (m/z): 1084.5353 are calculated；Actual measurement, 1084.7316.
Embodiment 7:
The device performance of provided using embodiment 3, structural formula such as formula 10 as object luminescent layer is verified, that is, to structure
Formula compound as shown in Equation 10 carries out performance verification as electroluminescent device prepared by object luminescent layer luminescent material.
ITO (tin indium oxide) glass phase after in cleaning agent and deionized water with ultrasonic cleaning 30 minutes.Then vacuum
Dry 2 hours (105 DEG C), then ITO (tin indium oxide) glass is put at the oxygen plasma for carrying out 5 minutes in plasma reactor
Reason, is transmitted in vacuum chamber and prepares organic film and metal electrode, and the sky of one layer of 10nm is then prepared by the method for vacuum evaporation
The hole mobile material of 40nm thickness: N, N'- bis- (1- naphthalene)-N, N'- diphenyl-is then deposited in hole injection material molybdenum trioxide
[1,1'- biphenyl] -4,4'- diamines (NPB), then upper one layer of 5nm hole barrier layer material: 1,3- bis- (9H- is steamed by vacuum evaporation
- 9 base of carbazole) benzene (mCP), then pass through the compound 9 in vacuum evaporation in the present invention of one layer of 20nm and be entrained in shining in mCP
Layer, doping concentration 10% then steam electron transport layer materials 1,3,5- tri- [(3- pyridyl group) -3- phenyl] benzene of upper 45nm
(TmPyPb), the Al of the LiF and 100nm of one layer of 1nm are finally deposited again.
The anode of direct current is added on ITO (tin indium oxide) layer, cathode is added on metal layer by cathode of the aluminium as device,
The bright uniform warm white issued from ITO layer can be obtained.This experiment apparatus structure are as follows: ITO (tin indium oxide)/MoO3
(10nm)/NPB (40nm)/mCP (5nm)/mCP:50%9 (20nm)/TmPyPb (45nm)/LiF (1nm)/Al (100nm).
Embodiment 8:
The device performance of provided using embodiment 3, structural formula such as formula 9 as object luminescent layer is verified, that is, to structural formula
Compound as shown in Equation 9 carries out performance verification as electroluminescent device prepared by object luminescent layer luminescent material.
ITO (tin indium oxide) glass phase after in cleaning agent and deionized water with ultrasonic cleaning 30 minutes.Then vacuum
Dry 2 hours (105 DEG C), then ITO (tin indium oxide) glass is put at the oxygen plasma for carrying out 5 minutes in plasma reactor
Reason, is transmitted in vacuum chamber and prepares organic film and metal electrode, and the sky of one layer of 10nm is then prepared by the method for vacuum evaporation
The hole mobile material of 40nm thickness: N, N'- bis- (1- naphthalene)-N, N'- diphenyl-is then deposited in hole injection material molybdenum trioxide
[1,1'- biphenyl] -4,4'- diamines (NPB), then upper one layer of 5nm hole barrier layer material: 1,3- bis- (9H- is steamed by vacuum evaporation
- 9 base of carbazole) benzene (mCP), then pass through the compound 9 in vacuum evaporation in the present invention of one layer of 20nm and be entrained in shining in mCP
Layer, doping concentration 50% then steam electron transport layer materials 1,3,5- tri- [(3- pyridyl group) -3- phenyl] benzene of upper 45nm
(TmPyPb), the Al of the LiF and 100nm of one layer of 1nm are finally deposited again.
The anode of direct current is added on ITO (tin indium oxide) layer, cathode is added on metal layer by cathode of the aluminium as device,
The near infrared light issued from ITO layer can be obtained.This experiment apparatus structure are as follows: ITO (tin indium oxide)/MoO3(10nm)/NPB
(40nm)/mCP (5nm)/mCP:50%9 (20nm)/TmPyPb (45nm)/LiF (1nm)/Al (100nm).
Test result is as follows:
It is compound doped in polymethyl methacrylate that Fig. 1 is that embodiment 3 provides, structural formula is as shown in Equation 9
(PMMA) the room temperature ultra-violet absorption spectrum in, room temperature and low-temperature photoluminescence spectra.The bright material of the chart is due to metal pair
The effect that ligand charge shifts (MCLT) state issues green light, since metal to metal is to the work of ligand charge transfer (MMLCT) state
With near infrared light is issued, multi-peak emission is presented.
Fig. 2 is the transient state spectrum longevity at the detection 502nm wavelength for the compound that embodiment 3 provides, structural formula is as shown in Equation 9
Life figure shows at 502nm wavelength as phosphorescent emissions.
Fig. 3 is the transient state spectrum longevity at the detection 708nm wavelength for the compound that embodiment 3 provides, structural formula is as shown in Equation 9
Life figure shows at 708nm wavelength as phosphorescent emissions and not identical as the mechanism of action at 502nm wavelength.
It is compound doped in polymethyl methacrylate that Fig. 4 is that embodiment 3 provides, structural formula is as shown in Equation 9
(PMMA) photoluminescence spectra of different temperatures in, show the material when by 502nm wavelength intensity normalize after, 708nm
Intensity at wavelength can be with the reduction and raising of temperature.Show light intensity at 708nm wavelength at temperature ratio 502nm wavelength more
Add sensitivity.
It is compound doped in polymethyl methacrylate that Fig. 5 is that embodiment 3 provides, structural formula is as shown in Equation 9
(PMMA) curve that the intensity at spectrum medium wavelength 708nm varies with temperature.The curve can be summarized as y=-0.0092x+
3.2108 trend, y are the intensity at 708nm, and x is absolute temperature.Should the result shows that the material with temperature linear change,
For the excellent material of temperature sensing.
Fig. 6 is the electroluminescent light spectrogram of the device for the compound that embodiment 7 provides, structural formula is as shown in Equation 9, is shown
The material can be prepared as unimolecule white light parts.
Fig. 7 is the device current ciency-luminance curve for the compound object that embodiment 7 provides, structural formula is as shown in Equation 9,
Show that the device has higher efficiency.
Fig. 8 is the electroluminescent light spectrogram of the device for the compound that embodiment 8 provides, structural formula is as shown in Equation 9, is shown
The material can be prepared as near infrared light device.
Fig. 9 is the device current ciency-luminance curve for the compound object that embodiment 8 provides, structural formula is as shown in Equation 9,
Show that the device has higher efficiency.
Other than design parameter employed in above-described embodiment, the present invention is directed to pyridines anthracene derivant platinum ligand compound
In the preparation method of object, the condition of each reaction step can also be adjusted flexibly, for example, flowing back in two step Suzuki coupling reactions
The temperature of heating 90 DEG C~110 DEG C, the reaction time, third step complexation reaction was heated at reflux at 9 hours~15 hours
Temperature control is controlled 130 DEG C~160 DEG C, reaction time at 48 hours~84 hours, this two steps Suzuki coupling reaction
In the proportions of various reaction raw materials, proportion of each reaction raw materials etc. can also be adjusted flexibly in third step complexation reaction；In addition,
Wet chemical (or aqueous sodium carbonate) its concentration and additive amount for providing alkaline environment can also be adjusted flexibly, only
The reaction system before reacting be heated at reflux in alkalinity.
Near infrared light in the present invention is the near infrared light on ordinary meaning, that is, wavelength is within the scope of 780~2526nm
Electromagnetic wave.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (11)
1. a kind of pyridines anthracene derivant iridium-platinum complex, which is characterized in that the pyridines anthracene derivant iridium-platinum complex
With the structure as shown in following formula formula (I):
Wherein, the R1For any one in H, F, Cl, Br；R2、R3For H and such as following formula formula (II), formula (III), formula
(IV) any one in group shown in；
2. pyridines anthracene derivant iridium-platinum complex as described in claim 1, which is characterized in that the pyridines anthracene derivant platinum
Complex has the structure as shown in formula (1)~formula (28) any one, wherein
For the formula (1), R1For H, R2、R3It is H；
For the formula (2), R1For F, R2、R3It is H；
For the formula (3), R1For Cl, R2、R3It is H；
For the formula (4), R1For Br, R2、R3It is H；
For the formula (5), R1For H, R2、R3It is the group as shown in the formula (II)；
For the formula (6), R1For F, R2、R3It is the group as shown in the formula (II)；
For the formula (7), R1For Cl, R2、R3It is the group as shown in the formula (II)；
For the formula (8), R1For Br, R2、R3It is the group as shown in the formula (II)；
For the formula (9), R1For H, R2、R3It is the group as shown in the formula (III)；
For the formula (10), R1For F, R2、R3It is the group as shown in the formula (III)；
For the formula (11), R1For Cl, R2、R3It is the group as shown in the formula (III)；
For the formula (12), R1For Br, R2、R3It is the group as shown in the formula (III)；
For the formula (13), R1For H, R2、R3It is the group as shown in the formula (IV)；
For the formula (14), R1For F, R2、R3It is the group as shown in the formula (IV)；
For the formula (15), R1For Cl, R2、R3It is the group as shown in the formula (IV)；
For the formula (16), R1For Br, R2、R3It is the group as shown in the formula (IV)；
For the formula (17), R1For H, R2For the group as shown in the formula (II), R3For the base as shown in the formula (III)
Group；
For the formula (18), R1For F, R2For the group as shown in the formula (II), R3For the base as shown in the formula (III)
Group；
For the formula (19), R1For Cl, R2For the group as shown in the formula (II), R3For the base as shown in the formula (III)
Group；
For the formula (20), R1For Br, R2For the group as shown in the formula (II), R3For the base as shown in the formula (III)
Group；
For the formula (21), R1For H, R2For the group as shown in the formula (II), R3For the base as shown in the formula (IV)
Group；
For the formula (22), R1For F, R2For the group as shown in the formula (II), R3For the base as shown in the formula (IV)
Group；
For the formula (23), R1For Cl, R2For the group as shown in the formula (II), R3For the base as shown in the formula (IV)
Group；
For the formula (24), R1For Br, R2For the group as shown in the formula (II), R3For the base as shown in the formula (IV)
Group；
For the formula (25), R1For H, R2For the group as shown in the formula (III), R3For the base as shown in the formula (IV)
Group；
For the formula (26), R1For F, R2For the group as shown in the formula (III), R3For the base as shown in the formula (IV)
Group；
For the formula (27), R1For Cl, R2For the group as shown in the formula (III), R3For the base as shown in the formula (IV)
Group；
For the formula (28), R1For Br, R2For the group as shown in the formula (III), R3For the base as shown in the formula (IV)
Group.
3. pyridines anthracene derivant iridium-platinum complex as claimed in claim 1 or 2, which is characterized in that be directed to the pyridines
The photoexcitation emission spectrum of anthracene derivant iridium-platinum complex has main peak in the emission peak and main peak of 500nm~600nm
In the emission peak of 700nm~800nm；The pyridines anthracene derivant iridium-platinum complex is entrained in polymethyl methacrylate
In.
4. pyridines anthracene derivant iridium-platinum complex as claimed in claim 3, which is characterized in that the main peak 500nm~
The emission peak of 600nm is based on metal in the pyridines anthracene derivant iridium-platinum complex to the work of ligand charge transfer state
With the main peak is based on metal pair in the pyridines anthracene derivant iridium-platinum complex in the emission peak of 700nm~800nm
Effect of the metal to ligand charge transfer state.
5. pyridines anthracene derivant iridium-platinum complex as claimed in claim 3, which is characterized in that when the main peak is in 500nm
Its main peak intensity of the emission peak of~600nm normalize when, the main peak its main peak intensity of the emission peak of 700nm~800nm with
The raising of temperature and reduce.
6. pyridines anthracene derivant iridium-platinum complex as claimed in claim 5, which is characterized in that the main peak 700nm~
Its main peak intensity of the emission peak of 800nm is to reduce as the temperature rises and linearly.
7. pyridines anthracene derivant iridium-platinum complex as claimed in claim 5, which is characterized in that the main peak 700nm~
Its main peak intensity of the emission peak of 800nm is reduced as the temperature rises and linearly within the temperature range of 77K~298K.
8. a kind of preparation method of pyridines anthracene derivant iridium-platinum complex, which comprises the following steps:
The preparation of (1) first raw material:
Under protective atmosphere, the first sub- reaction raw materials, the second sub- reaction raw materials, tetra-triphenylphosphine palladium are added to toluene solvant
In, and wet chemical or aqueous sodium carbonate are added into the toluene solvant, the first mixture is obtained after stirring；Then,
First mixture is carried out to be heated at reflux processing 9 hours~15 in 90 DEG C~110 DEG C under the protective atmosphere of flowing
Hour, it then cools down, and the isolated organic layer of organic solvent is added；Then, which is purified and is recrystallized
To the first solid, first solid i.e. the first raw material；
The ratio between mole of the first sub- reaction raw materials and the described second sub- reaction raw materials is no more than 1:2；First son is anti-
Raw material, the second sub- reaction raw materials is answered to be respectively provided with the structure being shown below:
The molar ratio of the tetra-triphenylphosphine palladium and the described first sub- reaction raw materials is 1:(10~100)；
First raw material has the structure being shown below:
(2) preparation of pyridines anthracene derivant:
Under protective atmosphere, first raw material, the second raw material, third raw material and four or three that the step (1) is obtained
Phenylphosphine palladium is added in toluene solvant, and wet chemical or aqueous sodium carbonate are added into the toluene solvant, stirring
After obtain the second mixture；Then, which is carried out under the protective atmosphere of flowing in 90 DEG C~110 DEG C
It is heated at reflux processing 9 hours~15 hours, is then cooled down, and the isolated organic layer of organic solvent is added；Then, this is organic
Layer is purified and is recrystallized to give the second solid, second solid, that is, pyridines anthracene derivant；
The ratio between mole of first raw material, second raw material and the third raw material three is 1:(1~1.5): (1
~1.5)；
Second raw material, the third raw material are respectively provided with the structure being shown below:
In the step (2), the molar ratio of the tetra-triphenylphosphine palladium and first raw material is 1:(10~100)；
The pyridines anthracene derivant has the structure being shown below:
(3) preparation of pyridines anthracene derivant iridium-platinum complex:
The pyridines anthracene derivant and platinum tetrachloride acid potassium that the step (2) obtains are added in acetic acid and obtain
Then three mixtures are filled with protective gas into the reaction vessel for accommodating the third mixture and exclude oxygen；Then, 130
DEG C~160 DEG C at be heated at reflux reaction 48 hours~84 hours, then cooling obtain third solid precipitate, the third solid
Precipitate, that is, pyridines anthracene derivant iridium-platinum complex；
The ratio between mole of the pyridines anthracene derivant and the platinum tetrachloride acid potassium is not less than 1:1.
9. the preparation method of pyridines anthracene derivant iridium-platinum complex as claimed in claim 8, which is characterized in that the protection
Property atmosphere be nitrogen or inert gas；The organic solvent in the step (1) and the step (2) is methylene chloride；
In the step (1), concentration of the first sub- reaction raw materials in first mixture is 1-20mmol/L；
In the step (2), concentration of first raw material in second mixture is 1-20mmol/L；
In the step (3), concentration of the pyridines anthracene derivant in the third mixture is 10-100mmol/L.
10. as described in claim 1-7 any one pyridines anthracene derivant iridium-platinum complex in temperature sensing device or
Application in organic electroluminescence device.
11. application as claimed in claim 10, which is characterized in that the organic electroluminescence device is white light parts or close red
Outer optical device.
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| "Bi-molecular emissive excited states in platinum (II) complexes for high-performance organic light-emitting diodes";J. Kalinowski等;《Chemical Physics》;20101209;第378卷(第1-3期);第47-57页 * |
| "Facile synthesis and platinum complexes of 4",5,5""-trisubstituted-2,2":6",2""-terpyridines";Jianqiang Huo等;《Dalton Transactions》;20110807;第40卷(第29期);第7534-7540页 * |
| "含有N^C^N三齿配体单元的环状化合物的合成及其Pt(II)配合物性能的研究";汤伟佳;《中国优秀硕士学位论文全文数据库·工程科技I辑》;20160515;全文 * |
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