CN106317122A - Platinum complex containing carbine structure and organic light-emitting diode using platinum complex - Google Patents
Platinum complex containing carbine structure and organic light-emitting diode using platinum complex Download PDFInfo
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Abstract
The invention provides a platinum complex containing a carbine structure and an organic light-emitting diode using the platinum complex. The structure of the platinum complex comprises a platinum metal ion, a zero-valent first nitrogen containing heterocyclic bidentate ligand, and a negative bivalent second nitrogen containing heterocyclic bidentate ligand. The first nitrogen containing heterocyclic bidentate ligand comprises at least one carbine part which is bonded with a platinum coordination bond. A second nitrogen containing heterocyclic bidentate ligand comprises at least one electron-withdrawing substituent, and the substituent and a central platinum metal ion form two nitrogen-platinum bonds or one nitrogen-platinum bond and one carbon-platinum bond. The platinum complex containing the carbine structure comprises the zero-valent first nitrogen containing heterocyclic bidentate ligand which comprises at least one carbine part that is bonded with the platinum coordination bond, wherein the carbine ligand has unoccupied molecular orbital with higher energy, can promote blue shift of emission wavelength, improves transition energy level of d-d track of the central platinum metal, and increases luminous efficiency, in order to obtain a blue light or green light material with high luminous efficiency.
Description
Technical field
The present invention relates to a kind of platinum complex being applicable to Organic Light Emitting Diode, particularly relate to a kind of tool carbon
The platinum complex of alkene structure and use the Organic Light Emitting Diode of this platinum complex, and be adapted to be formed
The double tooth aglucon of nitrogen heterocyclic ring at the tool carbene position of this kind of platinum complex.
Background technology
Organnic electroluminescent device generally comprises Organic Light Emitting Diode (organic light-emitting
Diode, hereinafter referred to as OLED) and drive element, wherein Organic Light Emitting Diode is being stimulated
After radiate the organic material of visible ray as luminescent layer.Luminescent layer mostly uses phosphor material, because it can
Utilize singlet excitons and triplet exciton simultaneously, and can effectively promote the luminous efficiency of OLED.
The blue light of the existing compound that wavelength is 470-530nm of giving out light the most by force efficiency of giving out light is the best.Example
As: United States Patent (USP) 6963005 disclose a kind of by the double tooth dentate of an oxygen-oxygen single anion, one
Four-coordination platinum (II) misfit that the double tooth dentate of carbon-phosphorus single anion chelates with platinum (II) central atom
Thing.Inorg.Chem., 2007,11202-then discloses four-coordination platinum (II) misfit thing [the Y table pyrrole shown in following formula
Azoles (pyrazole) or chlorine], the quantum yield (quantum yield) of its solid-state only up to 56%.
Summary of the invention
The present invention provides a kind of platinum complex having carbene structure and uses its Organic Light Emitting Diode, its
The luminous efficiency of OLED can be effectively promoted when the luminescent layer of OLED.
The present invention also provides for a kind of Organic Light Emitting Diode using this platinum complex.
The present invention also provides for being adapted to be formed the double tooth of nitrogen heterocyclic ring at the tool carbene position of this kind of platinum complex
Aglucon.
The structure of platinum complex of the tool carbene structure of the present invention includes: platinum ion, zeroth order
The double tooth aglucon of first nitrogen heterocyclic ring, and the double tooth aglucon of the second nitrogen heterocyclic ring of negative bivalence.First nitrogen heterocyclic ring
Double tooth aglucons have the carbene position of at least one and platinum coordination bond.The double tooth aglucon of second nitrogen heterocyclic ring has
At least one electron-withdrawing substituent, and form two nitrogen-platinum keys or a nitrogen-platinum key and with platinum ion
Individual carbon-platinum key.
In one embodiment of the present invention, the structure of the platinum complex of above-mentioned tool carbene structure is by leading to formula (I)
Or logical formula (II) represents:
Wherein X is CH or N, and RFFor-CmF2m+1, m is the integer of 1～7.
In one embodiment of the present invention, the structure of the double tooth aglucon of the first nitrogen heterocyclic ring is by formula (1), (2)
Or (3) represent:
Wherein R1For hydrogen, alkyl, the unsubstituted phenyl of carbon number 1～12 or be substituted phenyl, each R2Stand alone as carbon
The alkyl of several 1～6, each R3Stand alone as hydrogen, alkyl, the unsubstituted phenyl of carbon number 1～12 or be substituted benzene
Base, R4For hydrogen or the alkyl of carbon number 1～6, n is 1,2 or 3, the most wantonly two adjacent R3Ring can be linked to be.
In an embodiment of the present invention, the structure of the platinum complex of above-mentioned tool carbene structure by formula (I-1-1),
(I-1-2), (I-1-3), (I-1-4), (I-1-5) or (I-1-6) represents:
In one embodiment of the present invention, the structure of the platinum complex of above-mentioned tool carbene structure is by formula
(II-2-1)、(II-2-2)、(II-2-3)、(II-2-4)、(II-2-5)、(II-2-6)、(II-2-7)、(II-2-8)、(II-2-9)、
(II-2-10), (II-3-1), (II-3-2), (II-3-3), (II-3-4), (II-3-5) or (II-3-6) represents:
In one embodiment of the present invention, the structure of the platinum complex of above-mentioned tool carbene structure is by followingization
One of formula is represented:
The Organic Light Emitting Diode of the present invention includes two electrodes and the luminescence being configured between described two electrodes
Layer, described luminescent layer contains the platinum complex of above-mentioned tool carbene structure.
The structure of the double tooth aglucon of nitrogen heterocyclic ring at the tool carbene position of an embodiment of the present invention is by above-mentioned formula
(1) represent.
The structure of the double tooth aglucon of nitrogen heterocyclic ring at the tool carbene position of another embodiment of the present invention is by above-mentioned logical
Formula (2) represents.
The structure of the double tooth aglucon of nitrogen heterocyclic ring at the tool carbene position of a further embodiment of this invention is by above-mentioned logical
Formula (3) represents.
In the platinum complex of the tool carbene structure of the present invention, there is the carbon of at least one and platinum coordination bond
The double tooth aglucon of first nitrogen heterocyclic ring of the zeroth order at alkene position, these carbene aglucons are except the sky with higher-energy
Put track, emission wavelength blue shift can be made, it is possible to improve the transition energy level of the d-d track of center platinum,
And increase luminous efficiency, thus obtain blue light or the green light material of high-luminous-efficiency.
For the features described above of the present invention and advantage can be become apparent, special embodiment below, and coordinate
Accompanying drawing is described in detail below.
Accompanying drawing explanation
Fig. 1 illustrates the suction of the platinum complex with a carbene structure synthesized by the embodiment of the present invention 1～3
Receive spectrum and phosphorescence spectrum figure；
Fig. 2 illustrates the suction of the platinum complex with two carbene structures synthesized by the embodiment of the present invention 4～9
Receive spectrogram；
Fig. 3 illustrates the phosphorus of the platinum complex with two carbene structures synthesized by the embodiment of the present invention 4～9
Light spectrogram；
Fig. 4 illustrates the platinum complex with two carbene structures synthesized by the embodiment of the present invention 10～14
Absorption spectrum and phosphorescence spectrum figure.
Detailed description of the invention
Below will by embodiment, the invention will be further described, but such embodiment be only illustrate
Use is described, and is not used to limit the scope of the present invention.
The structure of the platinum complex of tool carbene structure
The structure of platinum complex of the tool carbene structure of the present invention includes: platinum ion, zeroth order
The double tooth aglucon of second nitrogen heterocyclic ring of the double tooth aglucons of the first nitrogen heterocyclic ring and negative bivalence.First nitrogen heterocyclic ring is double
Tooth aglucon has the carbene position of at least one and platinum coordination bond.The double tooth aglucon of second nitrogen heterocyclic ring has at least
One electron-withdrawing substituent, and form two nitrogen-platinum keys with platinum ion or form a nitrogen-platinum key and
Individual carbon-platinum key.
The double tooth aglucon of first nitrogen heterocyclic ring is e.g. by having the double of a carbene position represented by formula (1)
Tooth aglucon, formula (2) the double tooth aglucons with two carbene positions represented or represented by formula (3)
There are double tooth aglucons of two carbene positions and symmetry:
Wherein R1For hydrogen, alkyl, the unsubstituted phenyl of carbon number 1～12 or be substituted phenyl, each R2Stand alone as carbon
The alkyl of several 1～6, each R3Stand alone as hydrogen, alkyl, the unsubstituted phenyl of carbon number 1～12 or be substituted benzene
Base, R4For hydrogen or the alkyl of carbon number 1～6, n is 1,2 or 3, the most wantonly two adjacent R3Ring can be linked to be.
It addition, form the second nitrogen heterocyclic ring double tooth aglucon e.g. general of two nitrogen-platinum keys with platinum ion
Two protons of symmetrical nitrogen-containing heterocycle compound (4 ') shown below are pulled out and are obtained person, can be represented by below general formula (4).
Wherein X is CH or N, and RF is-CmF2m+1, and m is the integer of 1～7.This negative bivalence is double
Tooth aglucon is because being electron withdraw group containing pyrazole group and fluoroalkyl so can help to adjust platinum complex
HOMO energy level, making the difference of HOMO energy level and lumo energy meet, can radiate after exciting can
See the phosphorescence in light region, and can apply on Organic Light Emitting Diode.The platinum of the most above-mentioned tool carbene structure
Complex can be represented by below general formula (I) or logical formula (II):
Its formula of (I) has the double tooth aglucon of the first nitrogen heterocyclic ring of a carbene structure, e.g. by upper
State person represented by formula (1), logical formula (II) have the double tooth aglucon of the first nitrogen heterocyclic ring of two carbene structures,
E.g. by person represented by above-mentioned formula (2) or (3).
Some concrete instances of the tool carbene structure platinum complex meeting logical formula (I) are: by previously described formula
(I-1-1), (I-1-2), (I-1-3), (I-1-4), platinum complex represented by (I-1-5) or (I-1-6), hereinafter will
It is referred to as compound (I-1-1), (I-1-2) ....This kind of abbreviation mode is also applied mechanically and is changed with other below
Learn the platinum complex that structural formula is expressed.
Some concrete instances of the tool carbene structure platinum complex meeting logical formula (II) are: by previously described formula
(II-2-1)、(II-2-2)、(II-2-3)、(II-2-4)、(II-2-5)、(II-2-6)、(II-2-7)、(II-2-8)、
(II-2-9), (II-2-10), (II-3-1), (II-3-2), (II-3-3), (II-3-4), (II-3-5) or (II-3-6) institute
The platinum complex represented.
The double tooth aglucon of second nitrogen heterocyclic ring is not the tool carbene structure platinum network of the aglucon represented by above-mentioned formula (4)
Some concrete instances of compound are:
And
Wherein, the structure comparison of compound (III-2-1) is close to aforesaid compound (II-2-1), compound
(III-3-1) structure comparison is close to aforesaid compound (II-3-3), and the structure comparison of compound (III-3-2) is close
Aforesaid compound (II-3-5).
The Organic Light Emitting Diode of the present invention includes two electrodes and the luminescence being configured between this two electrode
Layer, this luminescent layer contains the platinum complex of above-mentioned tool carbene structure.The two respective materials of electrode can be selected for this
Usual user in field, also can add according to technology known in the art between each electrode and luminescent layer
Other functional layers.
The forming method of the platinum complex of tool carbene structure
The double tooth aglucon of first nitrogen heterocyclic ring is e.g. just formed when its predecessor reacts with platinum source.The
The predecessor of the double tooth aglucon of one nitrogen heterocyclic ring the most e.g. will have the compound of corresponding ring structure and necessary examination
Agent hybrid reaction and obtain.
Such as, the predecessor of two examples of the double tooth aglucon of the first nitrogen heterocyclic ring represented by formula (1) such as can be by
Step shown below is formed.
The tool carbene structure platinum complex of the present invention can select suitable reactant according to the change of each aglucon
And reaction condition is prepared, and reaction preparation method can become according to technology known in the art
Change.One concrete example of this platinum complex preparation method comprises the steps of and contains the first of tool carbene structure
The double predecessor of tooth aglucon of azacyclo-, platinum source and other necessary reagent mixing, then by products therefrom, second
The predecessor (the such as compound shown in previously described formula (4 ')) of the double tooth aglucon of nitrogen heterocyclic ring and other necessary examinations
Agent mixes, and heating is reacted.Double for first, second nitrogen heterocyclic ring tooth aglucons are connected with pt atom
Order can be reversed so that, i.e. first the predecessor of tooth aglucons double with the second nitrogen heterocyclic ring reacts nitrogenous with first again
The predecessor reaction of the double tooth aglucon of heterocycle.
The example first making the practice of pt atom and the double tooth aglucon connection of the first nitrogen heterocyclic ring is person shown below.
Embodiment
Below will by ten several embodiments, the invention will be further described, but such embodiment only as a example by
Show explanation use, and be not used to limit the scope of the present invention.
Embodiment 1
The preparation of compound (I-1-1):
Take the Pt (DMSO) of 300 milligrams (0.71mmol)2Cl2, 228 milligrams (0.75mmol)
1-methyl-3-(2-pyridine radicals) limidazolium hexafluorophosphate (1-methyl-3-(2-pyridyl) imidazolium
The sodium bicarbonate of hexafluorophosphate) and 120 milligrams (1.42mmol) is placed in two-neck bottle, with
The anhydrous dimethyl sulphoxide of 10 milliliters is solvent, and reaction temperature controls at 120 DEG C, will after reacting 19 hours
Temperature drops back to room temperature, adds the 5 of 203 milligrams (0.75mmol), double (the trifluoromethyl)-2H of 5'-, 2'H-3,3'-
Connection pyrazoles (5,5'-bis (trifluoromethyl)-2H, 2'H-3,3'-bipyrazole) and 117 milligram (1.42
Mmol) sodium acetate, reacts 12 hours in 120 DEG C, and reaction adds deionized water after terminating and cleans also
Filtering, collect filtering medium, can obtain product 210 milligrams after distillation, productivity is 45%.
The SPECTRAL DATA of compound (I-1-1): MS (FAB,195Pt):m/z 622[M+]；1H NMR(400
MHz,d6-dimethyl sulfoxide, 294K): δ 10.68 (br, 1H), 8.35 (br, 2H), 8.08 (br, 1H), 7.64
(br,1H),7.57(br,1H),6.65(br,1H),6.59(br,1H),4.45(s,3H)；19F NMR(376
MHz,d6-dimethyl sulfoxide, 294K): δ-58.87 (s, 3F) ,-59.34 (s, 3F).
Embodiment 2
The preparation of compound (I-1-3):
In addition to starting reactant difference, synthesis step is similar to compound (I-1-1), and productivity is 40%.
The SPECTRAL DATA of compound (I-1-3): MS (FAB,195Pt):m/z 678[M+]；1H NMR(400
MHz,d6-acetone 294K): δ 10.52 (d, J=6.3Hz, 1H), 8.47 (s, 1H), 8.02 (s, 1H), 7.65
(d, J=6.3Hz, 1H), 7.56 (s, 1H), 6.63 (s, 1H), 6.56 (s, 1H), 4.41 (s, 3H), 1.37 (s,
9H)；19F NMR(376MHz,d6-acetone, 294K): δ-58.83 (s, 3F) ,-59.31 (s, 3F).
The preparation of compound (I-1-5):
In addition to starting reactant difference, synthesis step is similar to compound (I-1-1), and productivity is 40%.
SPECTRAL DATA (I-1-5): MS (FAB,195Pt):m/z 706[M+]；1H NMR(400MHz,d6-
Acetone, 294K): δ 10.82 (d, J=6.3Hz, 1H), 8.30 (s, 1H), 8.00 (s, 1H), 7.73 (s, 1H),
7.59 (d, J=6.3Hz, 1H), 7.18～7.08 (m, 1H), 6.60 (s, 1H), 6.54 (s, 1H), 1.51 (d,
J=6.64Hz, 6H), 1.46 (s, 9H)；19F NMR(376MHz,d6-acetone, 294K): δ-69.24 (s,
3F),-71.13(s,3F)。
The absorption spectrum of the platinum complex with a carbene structure synthesized by embodiment 1～3 and phosphorescence light
Spectrum is illustrated in Fig. 1, and absworption peak position (abs λmax), emission peak positions (em λmax), quantum produce
Rate (φ) and phosphorescence vital stage (τ) are shown in table 1 below.
Table 1
| Compound | absλmax a(nm) | emλmax b(nm) | φb(%) | τb(ns) |
| (I-1-1) | 279,365 | 510 | 84.4 | 1126 |
| (I-1-3) | 280,340 | 552 | 93.8 | 780 |
| (I-1-5) | 280,340 | 501 | 94.7 | 1022 |
aUltraviolet light/visible light is in CH2Cl2Solution measures；bPhosphorescent characteristics measures under pulverulence.
From Fig. 1 and table 1, this three compound has an excellent luminous efficiency, about 85% to 95% it
Between, and its more general phosphorescent compound be short phosphorescence life cycle contribute to reduce triplet extinguishing send out
Raw, and then improve OLED luminous efficiency.Additionally the group of the alkyl functional on compound (I-1-5) modifies,
The making of the sublimability of molecule, beneficially element can be effectively increased.
Embodiment 4
The preparation of compound (II-2-1)
Take the Pt (DMSO) of 100 milligrams (0.23mmol)2Cl2, [the 1-(3 of 111 milligrams (0.24mmol)
'-(1 '-picolyl)-3-methyl] double the hexafluorophosphate ([1-(3 '-(1 ' of-imidazoles
-methylpyridiniumyl)-3-methyl]-imidazolium bishexafluorophosphate) and 40 milligrams
(0.48mmol) sodium bicarbonate is placed in two-neck bottle, with the anhydrous dimethyl sulphoxides of 4 milliliters as solvent, instead
Answer temperature to control at 110 DEG C, after reacting 12 hours, temperature is dropped back to room temperature, adds 70.4 milligram (0.26
Mmol) 5, double (the trifluoromethyl)-2H of 5'-, 2'H-3,3'-join pyrazoles, react 12 hours in 110 DEG C, react knot
Bundle removes solvent with vacuum system, and ethyl acetate is that developping solution carries out col-umn chromatography separation, further
Can obtain product 92 milligrams with dichloromethane recrystallization, productivity is 61%.
Data (II-2-1): MS (FAB,195Pt):m/z 636[M+]；1H NMR(400MHz,d6-two
Methyl sulfoxide, 298K): δ 8.60 (d, J=6.2Hz, 1H), 8.26～8.25 (br, 2H), 7.73 (dd, J=6.5
Hz, J=7.7Hz, 1H), 7.55 (d, J=2Hz, 1H), 6.60 (s, 1H), 6.56 (s, 1H), 4.69 (s, 3H),
4.48(s,3H)；19F NMR(376MHz,d6-dimethyl sulfoxide, 298K): δ-58.88 (s, CF3),
-58.94(s,CF3)。
Embodiment 5
The preparation of compound (III-2-1):
In addition to starting reactant and double tooth aglucon (the reacting predecessor) difference of the second nitrogen heterocyclic ring, close
Becoming step similar to compound (II-2-1), productivity is 69%.
The SPECTRAL DATA of compound (III-2-1): MS (FAB,195Pt):m/z 679[M+1+]；1H NMR
(400MHz,d6-dimethyl sulfoxide, 298K): δ 8.46 (d, J=6.2Hz, 1H), 8.26 (d, J=2Hz, 1H),
8.24 (d, J=7.92Hz, 1H) 7.69 (dd, J=6.5Hz, J=7.6Hz, 1H), 7.53 (d, J=1.92Hz,
1H),6.27(s,1H),6.26(s,1H),3.87(s,3H),3.66(s,3H),1.88(s,6H)；19F NMR
(376MHz,d6-dimethyl sulfoxide, 298K): δ-58.48 (s, 2 × CF3)。
Embodiment 6
The preparation of compound (II-2-3):
In addition to starting reactant difference, synthesis step is similar to compound (II-2-1), and productivity is 58%.
SPECTRAL DATA (II-2-3): MS (FAB,195Pt):m/z 737[M+1+]；1H NMR(400MHz,
d6-dimethyl sulfoxide, 298K): δ 8.61 (d, J=6Hz, 1H), 8.26～8.24 (br, 2H), 7.72 (dd,
J=6.4Hz, J=8Hz, 1H), 7.54 (d, J=2Hz, 1H), 6.66 (s, 1H), 6.61 (s, 1H), 4.68 (s,
3H),4.45(s,3H)；19F NMR(376MHz,d6-dimethyl sulfoxide, 298K): δ-83.20 (d,
J=56.4Hz, CF3)。
Embodiment 7
The preparation of compound (II-2-5):
In addition to starting reactant difference, synthesis step is similar to compound (II-2-1), and productivity is 64%.
The SPECTRAL DATA of compound (II-2-5): MS (FAB,195Pt):m/z 650[M+]；1H NMR(400
MHz,d6-dimethyl sulfoxide, 298K): δ 15.86 (br, 1H), 8.68 (t, J=5.84Hz, 1H), 8.35 (d,
J=7.96Hz, 1H), 8.30 (d, J=2.08Hz, 1H), 7.88 (d, J=2.12Hz, 1H), 7.69 (t, J=6.76
Hz, 1H), 6.88 (m, 1H), 6.78 (s, 1H), 6.69 (s, 1H), 1.48 (d, J=6.6Hz, 6H)；19F
NMR(376MHz,d6-dimethyl sulfoxide, 298K): δ-59.03 (s, CF3),-59.28(s,CF3)。
Embodiment 8
The preparation of compound (II-2-7):
In addition to starting reactant difference, synthesis step is similar to compound (II-2-1), and productivity is 59%.
The SPECTRAL DATA of compound (II-2-7): MS (FAB,195Pt):m/z 637[M+1+]；1H NMR(400
MHz,d6-dimethyl sulfoxide, 298K): δ 15.91 (br, 1H), 8.65 (t, J=5.88Hz, 1H), 8.33 (d,
J=7.88Hz, 1H), 8.23 (d, J=2.08Hz, 1H), 7.70～7.67 (br, 2H), 6.76 (s, 1H), 6.67 (s,
1H), 5.15 (q, J=7.04Hz, 2H), 1.39 (t, J=7Hz, 3H)；19F NMR(376MHz,d6-diformazan
Base sulfoxide, 298K): δ-59.00 (s, CF3),-59.06(s,CF3)。
Embodiment 9
The preparation of compound (II-2-9):
In addition to starting reactant difference, synthesis step is similar to compound (II-2-1), and productivity is 55%.
The SPECTRAL DATA of compound (II-2-9): MS (FAB,195Pt):m/z 736[M+]；1H NMR(400
MHz,d6-dimethyl sulfoxide, 298K): δ 15.91 (br, 1H), 8.53 (s, 1H), 8.29 (d, J=7.64Hz,
1H), 8.18 (s, 1H), 7.65～7.67 (br, 2H), 6.82 (s, 1H), 6.74 (s, 1H), 5.15 (q, J=6.88
Hz, 2H), 1.35 (t, J=7Hz, 3H)；19F NMR(376MHz,d6-dimethyl sulfoxide, 298K): δ
-83.14 (d, J=86.8Hz, CF3) ,-108.41 (d, J=376.92Hz, CF2)。
The absorption spectrum of the platinum complex with two carbene structures synthesized by embodiment 4～9 is illustrated in figure
2, phosphorescence spectrum is illustrated in Fig. 3, and absworption peak position (abs λmax), emission peak positions (em λmax)、
Quantum yield (φ) and phosphorescence vital stage (τ) are shown in table 2 below.
Table 2
| Compound | absλmax a(nm) | emλmax b(nm) | φb(%) | τb(ns) |
| (II-2-1) | 291,312,336 | 565 | 89 | 1247 |
| (III-2-1) | 306,337,359 | 462 | 16.2 | 7692 |
| (II-2-3) | 293,315,336 | 569 | 24 | 1520 |
| (II-2-5) | 289,330 | 535 | 78 | 883 |
| (II-2-7) | 290,331 | 532 | 96 | 852 |
| (II-2-9) | 293,316,335 | 543 | 99 | 841 |
aUltraviolet light/visible light is in CH2Cl2Solution measures；bPhosphorescent characteristics measures under pulverulence.
From Fig. 2,3 and table 2, this compounds has excellent luminous efficiency more, and has molecule
The structure of interior hydrogen bond can increase molecular rigidity, improves the photoluminescence quantum yield of compound, reaches as high as 99%,
It addition, the phosphorescence life cycle that its more general phosphorescent compound is short contributes to reducing sending out of triplet extinguishing
Raw, and then improve OLED luminous efficiency.
Embodiment 10
The preparation of compound (II-3-1):
Take the Pt (DMSO) of 300 milligrams (0.71mmol)2Cl2, 351 milligrams (0.75mmol)
1,1 '-dimethyl-3,3 ' the double hexafluorophosphate of-methylene-diimidazole
(1,1 '-dimethyl-3,3 '-methylene-diimidazolium bishexafluorophosphate) and 120
The sodium bicarbonate of milligram (1.42mmol) is placed in two-neck bottle, with the anhydrous dimethyl sulphoxides of 10 milliliters is
Solvent, reaction temperature controls at 120 DEG C, and temperature drops back to after reacting 19 hours room temperature, adds 203 millis
The 5 of gram (0.75mmol), double (the trifluoromethyl)-2H of 5'-, 2'H-3,3'-joins pyrazoles, in 120 DEG C of reactions 12
Hour, reaction terminates to remove solvent with vacuum system, and ethyl acetate/acetone (20:1) is that developping solution enters
Line pipe column chromatography for separation, further can obtain product 297 with ethyl acetate and hexane mixed solution recrystallization
Milligram, productivity is 65%.
The SPECTRAL DATA of compound (II-3-1): MS (FAB,195Pt):m/z 639[M+]；1H NMR(500
MHz,d6-dimethyl sulfoxide, 294K): δ 7.64 (d, J=2.0Hz, 2H), 7.46 (d, J=2.0Hz, 2H),
6.52 (s, 2H), 6.20 (d, J=13.0Hz, 1H), 6.10 (d, J=13.0Hz, 1H), 3.97 (s, 6H)；19F
NMR(470MHz,d6-dimethyl sulfoxide, 294K): δ-59.11 (s, 6F).
Embodiment 11
The preparation of compound (II-3-3):
In addition to starting reactant difference, synthesis step is similar to compound (II-3-1), and productivity is 70%.
(II-3-3) SPECTRAL DATA: (FAB,195Pt):m/z 695[M+]；1H NMR(500MHz,d6-two
Methyl sulfoxide, 294K): δ 7.65 (d, J=2.0Hz, 2H), 7.64 (d, J=2.0Hz, 2H), 6.53 (s, 2H),
6.18 (d, J=13.5Hz, 1H), 6.09 (d, J=13.5Hz, 1H), 5.32 (m, J=6.5Hz, 2H), 1.60 (d,
J=6.5Hz, 6H), 1.15 (d, J=6.5Hz, 6H)；19F NMR(470MHz,d6-dimethyl sulfoxide,
294K):δ-59.25(s,6F)。
Embodiment 12
The preparation of compound (III-3-1):
In addition to starting reactant and double tooth aglucon (the reacting predecessor) difference of the second nitrogen heterocyclic ring, close
Becoming step similar to compound (II-3-1), productivity is 48%.
The SPECTRAL DATA of compound (III-3-1): MS (FAB,195Pt):m/z 649[M+]；1H NMR(500
MHz,d6-dimethyl sulfoxide, 294K): δ 7.62 (d, J=2.5Hz, 1H), 7.58 (d, J=2.0Hz, 1H),
7.48 (d, J=2.5Hz, 1H), 7.42 (d, J=7.5Hz, 1H), 7.37 (d, J=2.0Hz, 1H), 7.33 (s,
1H), 7.23 (d, J=7.5Hz, 1H), 6.60 (s, 1H), 6.15 (d, J=13.0Hz, 1H), 6.00 (d, J=13.0
Hz,1H),3.99(s,3H),3.70(s,3H)；19F NMR(470MHz,d6-dimethyl sulfoxide, 294K): δ
-59.00(s,3F),-60.77(s,3F)。
Embodiment 13
The preparation of compound (II-3-5):
In addition to starting reactant difference, synthesis step is similar to compound (II-3-1), and productivity is 58%.
SPECTRAL DATA (II-3-5): MS (FAB,195Pt):m/z 723[M+]；1H NMR(400MHz,d6-
Dimethyl sulfoxide, 294K): δ 7.50 (d, J=1.5Hz, 2H), 7.40 (d, J=1.5Hz, 2H), 6.48 (s, 2H),
5.26 (sp, J=6.5Hz, 2H), 4.72 (dd, J=14.5,11Hz, 2H), 4.32 (dd, J=14.5,6Hz, 2H),
2.33～2.28 (m, 1H), 1.88～1.80 (m, 1H), 1.38 (d, J=6.5Hz, 6H), 1.35 (d, J=6.5Hz,
6H)；19F NMR(470MHz,d6-dimethyl sulfoxide, 294K): δ-58.87 (s, 6F).
Embodiment 14
The preparation of compound (III-3-2):
In addition to starting reactant and double tooth aglucon (the reacting predecessor) difference of the second nitrogen heterocyclic ring,
Synthesis step is similar to compound (II-3-1), and productivity is 63%.
The SPECTRAL DATA of compound (III-3-2): MS (FAB,195Pt):m/z 733[M+]；1H NMR(500
MHz,d6-dimethyl sulfoxide, 294K): δ 7.50 (d, J=2.0Hz, 1H), 7.42～7.37 (m, 3H), 7.32
(d, J=2.0Hz, 1H), 7.19 (d, J=7.5Hz, 1H), 6.57 (s, 2H), 5.21 (sp, J=6.5Hz, 1H),
5.11 (sp, J=6.5Hz, 1H), 4.69 (dd, J=14.0,11.0Hz, 1H), 4.57 (dd, J=14.0,11.0Hz,
1H), 4.31～4.21 (m, 2H), 2.32～2.25 (m, 1H), 1.84～1.76 (m, 1H), 1.44 (d, J=6.5Hz,
3H), 1.33 (d, J=6.5Hz, 3H), 1.29 (d, J=6.5Hz, 3H), 1.24 (d, J=6.5Hz, 3H)；19F
NMR(470MHz,d6-dimethyl sulfoxide, 294K): δ-58.72 (s, 3F) ,-60.83 (s, 2F).
The absorption spectrum of the platinum complex with two carbene structures synthesized by embodiment 10～14 and phosphorescence
Spectrum is illustrated in Fig. 4, and absworption peak position (abs λmax), emission peak positions (em λmax), quantum
Productivity (φ) and phosphorescence vital stage (τ) are shown in table 3 below.
Table 3
| Compound | absλmax a(nm) | emλmax b(nm) | φb(%) | τb(μs) |
| (II-3-1) | 263,280,294 | 418,441,466 | 50 | 29 |
| (II-3-3) | 262,279,292 | 422,444,470 | 50 | 33 |
| (III-3-1) | 273,298,321 | 464,491,520 | 96 | 22 |
| (II-3-5) | 268 | 398,421,446 | 70 | 21,46 |
| (III-3-2) | 258,290,312,330 | 455,482,514 | 100 | 41 |
aUltraviolet light/visible light measures in dimethyl sulphoxide solution；bPhosphorescent characteristics measures under pulverulence.
From Fig. 4 and table 3, this compounds has good blue light emitting character, wherein (III-3-2)
And (III-3-1) not only shows the performance as Nan dian Yao dopant material, more there is high luminous table
Existing, the quantum yield of respectively 96% and 100%.
Embodiment 15
The preparation of compound (II-3-4):
In addition to starting reactant difference, synthesis step is similar to compound (II-3-1), and productivity is 65%
(II-3-4) SPECTRAL DATA: MS (FAB, 195Pt): m/z 705 [M+]；1H NMR(500MHz,
D6-dimethyl sulfoxide 294K): δ 7.72 (d, J=2.0Hz, 2H), 7.71 (d, J=2.0Hz, 2H), 6.23
(d, J=13.0Hz, 1H), 6.15 (d, J=13.0Hz, 1H), 5.13 (sp, J=6.5Hz, 2H), 1.63 (d,
J=6.5Hz, 6H), 1.19 (d, J=6.5Hz, 6H)；19F NMR (470MHz, d6-dimethyl sulfoxide,
294K):δ-63.18(s,6F)。
In sum, present invention uses the carbene high field dentate being bond atom with carbon, these aglucons
Except there is the vacant track of higher-energy, emission wavelength blue shift can being made, also can effectively raise misfit thing
D-d track transition energy level, makes Pt misfit thing still have good blue light or green when there being molecular stacks
Light luminous efficiency.And by modified with functional group different in dentate, adjustable luminescence is photochromic, and utilizes
The formation of intramolecular hydrogen bond improves rigidity, therefore quantum yield reaches as high as 100%.And change the alkyl of carbene
The carbon number of functional group can improve the sublimability of this compound, coordinates the character of low-phosphorous smooth life cycle, reduces
The chance of occurrence of triplet extinguishing, can fully improve the performance of element.
Last it is noted that various embodiments above is only in order to illustrate technical scheme, rather than right
It limits；Although the present invention being described in detail with reference to foregoing embodiments, this area common
Skilled artisans appreciate that the technical scheme described in foregoing embodiments still can be repaiied by it
Change, or the most some or all of technical characteristic is carried out equivalent；And these are revised or replace
Change, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. the platinum complex having carbene structure, it is characterised in that the platinum network of described tool carbene structure
The structure of compound includes: platinum ion, the double tooth aglucons of the first nitrogen heterocyclic ring of zeroth order and negative bivalence
The double tooth aglucon of the second nitrogen heterocyclic ring, wherein the double tooth aglucon of the first nitrogen heterocyclic ring has at least one and joins with platinum
The carbene position of position bond, the double tooth aglucon of the second nitrogen heterocyclic ring has at least one electron-withdrawing substituent, and with
Platinum ion forms two nitrogen-platinum keys or a nitrogen-platinum key and a carbon-platinum key.
The platinum complex of tool carbene structure the most according to claim 1, it is characterised in that described
The structure of the platinum complex of tool carbene structure is by leading to formula (I) or logical formula (II) represents:
Wherein X is CH or N, and RFFor-CmF2m+1, m is the integer of 1～7.
The platinum complex of tool carbene structure the most according to claim 1 and 2, it is characterised in that institute
The structure stating the double tooth aglucon of the first nitrogen heterocyclic ring is represented by formula (1), (2) or (3):
Wherein R1For hydrogen, alkyl, the unsubstituted phenyl of carbon number 1～12 or be substituted phenyl, each R2Stand alone as
The alkyl of carbon number 1～6, each R3Stand alone as hydrogen, alkyl, the unsubstituted phenyl of carbon number 1～12 or be substituted benzene
Base, R4For hydrogen or the alkyl of carbon number 1～6, and n is 1,2 or 3, the most wantonly two adjacent R3Can connect to
Ring.
The platinum complex of tool carbene structure the most according to claim 3, it is characterised in that described
The structure of the platinum complex of tool carbene structure is by formula (I-1-1), (I-1-2), (I-1-3), (I-1-4), (I-1-5)
Or (I-1-6) represents:
The platinum complex of tool carbene structure the most according to claim 3, it is characterised in that institute
State tool carbene structure platinum complex structure by formula (II-2-1), (II-2-2), (II-2-3),
(II-2-4)、(II-2-5)、(II-2-6)、(II-2-7)、(II-2-8)、(II-2-9)、(II-2-10)、
(II-3-1), (II-3-2), (II-3-3), (II-3-4), (II-3-5) or (II-3-6) represents:
The platinum complex of tool carbene structure the most according to claim 1, it is characterised in that described
The structure of the platinum complex of tool carbene structure is represented by one of below formula:
7. an Organic Light Emitting Diode, it is characterised in that include two electrodes and be configured at described two electricity
A luminescent layer between pole, described luminescent layer contains the tool carbene as according to any one of claim 1～6
The platinum complex of structure.
8. the double tooth aglucon of nitrogen heterocyclic ring having carbene position, it is characterised in that by formula (1) table
Show:
Wherein R1For hydrogen, alkyl, the unsubstituted phenyl of carbon number 1～12 or be substituted phenyl, R2For carbon number
The alkyl of 1～6, and each R3Stand alone as hydrogen, alkyl, the unsubstituted phenyl of carbon number 1～12 or be substituted benzene
Base, wherein two R3Cyclization can be linked.
9. the double tooth aglucon of nitrogen heterocyclic ring having carbene position, it is characterised in that by formula (2) table
Show:
Wherein R2For the alkyl of carbon number 1～6, each R3Stand alone as hydrogen, carbon number 1～12 alkyl, unsubstituting phenenyl
Base or be substituted phenyl, and R4For hydrogen or the alkyl of carbon number 1～6, wherein two R3Cyclization can be linked.
10. the double tooth aglucon of nitrogen heterocyclic ring having carbene position, it is characterised in that by formula (3) table
Show:
The most each R2Stand alone as the alkyl of carbon number 1～6, each R3Stand alone as hydrogen, the alkyl of carbon number 1～12,
Unsubstituted phenyl or be substituted phenyl, and n is 1,2 or 3, the most wantonly two adjacent R3Can connect to
Ring.
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| CN101087863A (en) * | 2004-12-23 | 2007-12-12 | 西巴特殊化学品控股有限公司 | Electroluminescent metal complexes with nucleophilic carbene ligands |
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| US20100007273A1 (en) * | 2004-05-18 | 2010-01-14 | Peter Djurovich | Carbene metal complexes as oled materials |
| CN101087863A (en) * | 2004-12-23 | 2007-12-12 | 西巴特殊化学品控股有限公司 | Electroluminescent metal complexes with nucleophilic carbene ligands |
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