CN105017329B - Tridentate anionic ligand-based europium complex luminescent material - Google Patents
Tridentate anionic ligand-based europium complex luminescent material Download PDFInfo
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- CN105017329B CN105017329B CN201510435508.9A CN201510435508A CN105017329B CN 105017329 B CN105017329 B CN 105017329B CN 201510435508 A CN201510435508 A CN 201510435508A CN 105017329 B CN105017329 B CN 105017329B
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- 0 *C(C=C*1)=C(*2)C1=CC=C2N Chemical compound *C(C=C*1)=C(*2)C1=CC=C2N 0.000 description 5
- HMOQPXSMHBJRDD-UHFFFAOYSA-N CC[O](C(C)(C)C)(C(C)(C)C)N Chemical compound CC[O](C(C)(C)C)(C(C)(C)C)N HMOQPXSMHBJRDD-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a rare earth europium complex luminescent material based on a tridentate anionic ligand and a preparation method and application thereof. The structural general formula of the europium complex is Eu (t-ND)3Wherein t-ND is phosphino, sulfoxide or sulfone substituted 4-hydroxy-1, 5-naphthyridine tridentate anion ligand. The europium complex has a more rigid structure, a high coordination stability constant, difficulty in ligand dissociation and a high thermal decomposition temperature;the phosphine atom and the sulfur atom are hybridized by sp3 without strong conjugation effect, so that the ligand is ensured to have proper energy level, and the complex also has high luminous efficiency; in addition, the europium complex has good ultraviolet light tolerance and high electron and hole mobility, and can be used as a down-conversion photoluminescence material and an organic electroluminescence material.
Description
Technical field
The present invention relates to a kind of Rare Earth Europium Complex luminescent material and preparation method thereof, and in luminescence generated by light and electroluminescent hair
Application in optical arena.
Background technology
Rare-earth complexes luminous material has unique advantage such as luminous efficiency height, long lifespan, high color purity, illumination,
There is important application prospect in the fields such as display, conversion film, biomedicine.As a kind of embedded photoluminescent material, due to organic
Part has very big molar absorption coefficient, so (such as Y compared with purely inorganic material2O3：Eu3+), the suction of rare earth compounding
Light ability can increase hundreds of times, and the consumption of rare earth can also greatly reduce.Moreover, rare earth compounding has preferably with macromolecule
Compatibility, than inorganic material more suitable for use in terms of functional conversion film, such as agricultural conversion film, solar cell light are changed
In film.In addition, application of the rare earth compounding in electroluminescent (Organic Light-emitting Diode, OLED)
It is the primary study direction of people, and rare earth luminous also has an opportunity to show body in bright-coloured, ultra-thin, flexible OLED display fields one
Hand.
In rare earth compounding, organic ligand serves conclusive effect for the luminosity of complex.It is organic to match somebody with somebody
Body and rare earth ion are chelated, and can not only be absorbed as antenna and be transmitted energy, and can protect it is rare earth luminous not by
External environment is quenched.In traditional Rare Earth Europium Complex the most frequently used part be beta-diketone compounds, this kind of material since
The sixties in last century is just studied in large quantities, and the material for also having many luminous efficiencies high so far is also developed.But
Application of the rare earth compounding in terms of illumination, display and conversion film does not have to be promoted on a large scale, and its main cause is just
Be material photostability it is too poor.Usual rare earth compounding absorbs the energy of ultraviolet light and excited, but beta-diketon class
Compound is but easily destroyed by the ultraviolet of high energy in itself, causes the rapid decay of material emission performance
(Synth.Met.2011,161,964).
In recent study, inventor has found and devises class 4- hydroxyl -1,5- naphthyridines (abbreviation ND) class part, and
It is coordinated with europium ion, has obtained a kind of efficient rare earth luminescent material (CN 201110139842.1).Such part has rigidity
Molecular structure and suitable sensitization energy level, resulting complex not only has high photoluminescence quantum efficiencies (PLQY),
And show outstanding photostability.But, in practical application, it has been found that this kind of rare earth compounding still has heat endurance
The defect of aspect.Such ND part is mainly two tooth anion ligands, so we are in synthetic compound, except using three
Beyond individual ND classes part, it can also use some neutral ligands rare earth ion is reached coordination saturation, prevent solvent molecule or water
Molecular complexes cause luminous be quenched.But it is due to that neutral ligand and rare earth ion adhesion are weaker, in weak solution or heating etc.
Under extreme condition, easily occur dissociating and causing the destruction of complex and the decay of luminosity.Such as in vacuum steaming plating method
During preparing OLED, the solution defection of neutral ligand causes substantially reducing for device efficiency.So this kind of rare earth coordinates
The still needing to of thing luminescent material makes necessary improvement so that it possesses superior technique effect and wider application prospect.
The content of the invention
Easily dissociate the invention aims to solving existing rare earth compounding neutral ligand, the technology of stability difference it is difficult
Topic, obtains the rare earth luminescent material that a kind of luminous efficiency is high, thermally-stabilised and light is stable.
As described in technical background above, the synthesis of two tooth ND class rare earth compoundings usually requires to carry using neutral ligand
Its high luminous efficiency, but brings the technological deficiency that neutral ligand is easily dissociated, thermal analysis is poor.The solution of the present invention
Thinking be design synthesizing new three tooth ND anionoid parts, by increasing the chelating site of part, when by 3: 1 with rare earth from
Son is formed after complex, it is possible to meet the requirement of coordination saturation (ligancy is 9), it is to avoid neutral ligand introduces the heat brought
Stability problem, so as to obtain thermally-stabilised, light stabilization and efficient rare-earth complexes luminous material.
In general, when people design the group chelated with rare earth ion, azepine aryl, acid amides, the carboxylic generally used
Base etc..But for ND class parts, by increasing, above-mentioned group obtains tridentate ligand and improper, because these bases
Group can be conjugated with naphthyridines ring and cause substantially reducing for part energy, it is possible to can reduce sensitization efficiency and luminous efficiency.In order to
Part energy level is not influenceed, and the present invention devises new chelation group, respectively phosphine epoxide, sulfoxide group and sulfuryl.These groups
In phosphorus atoms and sulphur atom all use sp3 hydridization, so the conjugation between naphthyridines ring weakens significantly, to part energy level
Influence it is also not too large.
Specifically, technical scheme is as follows：
One kind is based on the rare earth compounding of three tooth 4- hydroxyl -1,5- naphthyridine type parts, and general structure is Eu (t-ND)3, its
Middle t-ND is 4- hydroxyl -1,5- naphthyridine type anion ligands of the phosphine epoxide substitution shown in Formulas I, the sulfoxide group substitution shown in Formula II
4- hydroxyl -1,5- naphthyridine type anion ligands, or shown in formula III sulfuryl substitution 4- hydroxyl -1,5- naphthyridines anionoids
Part.
The structure of the europium complex is as shown in formula IV, Formula V and Formula IV：
In Formulas I-VI, R1、R2、R3、R4Each stand alone as hydrogen atom, halogen atom, cyano group, alkyl, halogen-substituted alkyl,
Phenyl.Wherein, the halogen atom refers to F, Cl, Br, I；The straight or branched alkyl of the preferred C1-C8 of alkyl, more preferably C1-
C4 straight or branched alkyl, including methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, it is especially excellent
Select methyl, ethyl and the tert-butyl group；The C1-C8 of the preferred halogen substitution of halogen-substituted alkyl straight or branched alkyl, it is more excellent
Select the C1-C4 of halogen substitution straight or branched alkyl, particularly preferred trifluoromethyl, pentafluoroethyl group.
In Formulas I-VI, R5For alkyl, aryl.Wherein, the preferred C1-C18 of alkyl straight or branched alkyl, especially excellent
Select methyl, ethyl, n-propyl, isopropyl, normal-butyl, the tert-butyl group, n-octyl, dodecyl, n-hexadecyl, n-octadecane
Base；The aryl is phenyl, naphthyl or substituted phenyl；The substituted phenyl is by halogen atom, methyl, ethyl, isopropyl
The phenyl that base, the tert-butyl group, methoxyl group, ethyoxyl, trifluoromethyl, dimethylamino are replaced, the number of substituent and position can roots
Depending on actual conditions, preferably 2- fluorophenyls, 2- chlorphenyls, 2- bromophenyls, 3- fluorophenyls, 3- chlorphenyls, 3- bromophenyls, 4- fluorine
Phenyl, 4- chlorphenyls, 4- bromophenyls, 2,3- dichlorophenyls, 2,4- dichlorophenyls, 2,5- dichlorophenyls, 2,6- dichlorophenyls, 3,
4- dichlorophenyls, 3,5- dichlorophenyls, 2- aminomethyl phenyls, 2- ethylphenyls, 2- isopropyl phenyls, 2- tert-butyl-phenyls, 4- first
Base phenyl, 4- ethylphenyls, 4- isopropyl phenyls, 4- tert-butyl-phenyls, 2,4- 3,5-dimethylphenyls, 2,5- 3,5-dimethylphenyls, 2,
6- 3,5-dimethylphenyls, 3,5- 3,5-dimethylphenyls, 2- methyl -5- tert-butyl-phenyls, 2- methoxyphenyls, 3- methoxyphenyls, 4-
Methoxyphenyl, 2- dimethylamino phenyls, 4- dimethylamino phenyls, particularly preferred 2- chlorphenyls, 2- aminomethyl phenyls, 4- methylbenzenes
Base, 2- methoxyphenyls, 3- methoxyphenyls, 4- methoxyphenyls.
Heretofore described three new tooth anion ligands and the europium based on this kind of three teeth anion ligand coordinate
Thing is all in the protection domain of the patent.
The form of three heretofore described tooth anion ligands can be neutral, the salt to be formed is reacted with acid or alkali,
Compound comprising the crystallization water or solvent, the salt obtained with acid or alkali reaction are while the compound comprising solvent or the crystallization water.
There is the tautomerism of keto-acid and enol form in three heretofore described tooth anion ligands, multi-form mutually makes a variation
Structure body is all in the protection domain of this patent.Tautomeric form is as follows：
The form of heretofore described europium complex can be sterling or the compound comprising the crystallization water or solvent.
The preparation method of three tooth anion ligands in the present invention, is matched somebody with somebody as the ND classes that the 6- positions halogen shown in Formula VII replaces
Body and the organic chloride phosphine shown in Formula VIII or the thiol reactant shown in Formula IV V, are coupled by first step nucleophilic displacement of fluorine,
Second step oxidation is obtained.
R in Formula VII1-R4Described in group face as defined above, X represents halogen atom F, Cl, Br, I；Formula VIII and formula
R in VIV5Described in group face as defined above.
Specifically, the ND anionoid part synthesis steps of the phosphine epoxide substitution shown in Formulas I are as follows, are defined as route a
(Scheme a)：
The ND anionoids part and synthesis step of sulfoxide and sulfuryl substitution shown in Formula II and formula III are as follows, definition
For route b (Scheme b)：
In route a and route b, first, proton, organic chloride phosphine are captured in ND classes part and the alkali reaction of 6- halogen substitutions
Or mercaptan obtains corresponding salt with alkali metal reaction, then carries out coupling reaction；MOH represents the hydroxide of alkali metal formation
Thing, such as lithium hydroxide, sodium hydroxide, potassium hydroxide；M represents lithium metal, sodium, potassium.
In route a and route b, the solvent used in coupling reaction includes ether, tetrahydrofuran, toluene, dimethylbenzene, ethylene glycol
Dimethyl ether etc.；The temperature of reaction is temperature of the room temperature to solvent refluxing；Reaction time is 1~24 hour.
In route a and route b, [O] in oxidation reaction represents oxidant, including oxygen, ozone, chlorine, chlorine water, secondary chlorine
Sour sodium, peroxide acids (such as perbenzoic acid, m-chloro-benzoic acid peroxide, Peracetic acid), hydrogen peroxide.
The preparation method of europium complex in the present invention, using ND classes part, alkali and the europium salt of Formulas I (or II, III) in solvent
Middle reaction, is made the europium complex shown in formula IV (or V, VI).The preferred hydroxide of described alkali, carbonate or amine, pyrrole
Pyridine class organic base, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammoniacal liquor, triethylamine, TMAH.
Described hydrochloride, nitrate, acetate, trifluoro sulfonate of the preferred europium of europium salt etc..In methods described, Formulas I (or II, III)
ND classes part, the mol ratio of alkali and europium reactant salt be 3: 3: 1, or close to the mol ratio.In methods described, the temperature of reaction
For -10~120 DEG C, the time is 10 minutes~24 hours.Described solvent is selected from water, ethanol, methanol, isopropanol, acetone, tetrahydrochysene
Furans, acetonitrile, toluene, dichloromethane, chloroform, ether, DMF etc., can be any of which or
Person is the mixture of two kinds and the above.
Europium complex of the present invention includes two aspects of luminescence generated by light and electroluminescent as the application of luminescent material.
In terms of luminescence generated by light, this kind of europium complex can be used to construct the down-conversion luminescent material with practical use.
Its application mode includes：(1) use in solid form, such as solid powder, or formation after solvent is removed using solution spraying
Film etc.；(2) be entrained in certain matrix and use, such as solution, ink, ionic liquid, high molecule plastic, colloid or
In other solid materials.This kind of luminescent material can be obtained under in ultraviolet light, either blue violet light is excited bright feux rouges or
The luminous of blend color can be obtained after being mixed with other fluorescers.
In electroluminescent fermentation, this kind of europium complex (in the form of pure compound or is entrained in other material of main parts
In) by the method formation ultrathin membrane of vacuum evaporation, spin coating or inkjet printing, as luminous in organic electroluminescence device
Layer material.Electroluminescent device based on this kind of europium complex can send the feux rouges of feature under electric current driving, or and its
He is used in conjunction with the luminescent material of color, can obtain the luminous or white light of multiple color.
Heretofore described europium complex has advantages below：(1) without using other neutral ligands, neutrality is solved
The destabilizing factor that part is easily dissociated；(2) three tooth chelating ligands, complexation constant is big, and coordination ability is strong, and part itself is not easy
Dissociation；(3) rare-earth ion coordination saturation, the quenching effect without other solvent molecules, luminous quantum efficiency is high；(4) ND classes are matched somebody with somebody
Body has rigid structure, and the ultraviolet light tolerance of material is strong, and heat decomposition temperature is high；(5) ND classes part has aromatic heterocyclic
Structure, carrier mobility is high, has advantage in electroluminescent application.
Specifically, heretofore described ND classes tridentate ligand has suitable sensitization energy level and rigid structure, institute
Obtained europium complex is with very high photoluminescence quantum yield, the europium complex Eu3 that such as embodiment 3 is obtained, and it is consolidated
The PLQY of body powder is up to 94%, and the row of highest level are in compared with europium complex reported in the literature.It is of the present invention
Europium complex also has high ligand stability constant, the solid powder of this kind of europium complex is placed in strong acid or strong base solution long
Time is soaked all without the disappearance for causing luminescent properties.In addition, heretofore described europium complex also has good heat steady
The europium complex Eu5 that qualitative and photostability, such as embodiment 5 are obtained, its heat decomposition temperature is up to 440 degrees Celsius, Er Qie
The irradiation of 40 watts of UVA340 type uviol lamps does not cause obvious light degradation in lower 20 hours.Based on this kind of europium complex (Eu3)
Electroluminescent device also there is good performance, PRELIMINARY RESULTS shows that high-high brightness is up to 1180cdm-2, maximum current efficiency
For 14cdA-1.In a word, europium complex of the invention has very excellent luminosity and outstanding stability, with tradition or
The incomparable advantage of known europium complex luminescent material, in terms of fluorescent pigment, conversion film, biomarker, electroluminescent
All there is very major application prospect, be a kind of rare outstanding rare earth luminescent material.
Brief description of the drawings
Fig. 1 is absorption spectrums of the obtained europium complex Eu3 of the embodiment of the present invention 3 in dichloromethane solution.
Fig. 2 is exciting and emission spectrum for the europium complex Eu3 solid powders that the embodiment of the present invention 3 is obtained.
Fig. 3 be the embodiment of the present invention 12 electroluminescent device in used associated materials structural formula.
Fig. 4 is current density-luminance-voltage figure of the electroluminescent device of the embodiment of the present invention 12.
Fig. 5 is the electroluminescent device of the embodiment of the present invention 12 in 100cdm-2When emission spectrum.
Embodiment
Product of the invention, preparation method and applications are further described below by specific embodiment, but this
A little specific embodiments are not in any way limit the scope of the present invention.
The ND classes part (1a, 2a, 3a) of 6- positions halogen substitution in following examples can use patent of invention
Method synthesis in CN201110139842.1, organic chloride phosphine, mercaptan and other agents useful for same can be bought from Reagent Company.Institute
The solvent used is pure to analyze, and other reagents are pure for chemistry.
<The synthesis of part and complex>
Embodiment 1.
The synthetic route being related in the present embodiment is as follows：
1.1 ligand 1 f (4- hydroxyl -6- diethyl phosphine Oxy-1s, 5- naphthyridines, 4-hydroxy-6-
(diethylphosphoryl) -1,5-naphthyridine) synthesis
Chloro- 1, the 5- naphthyridines (1a) of 4- hydroxyls -6- and NaOH reactions are obtained into its sodium salt 1b.By 30mmol diethyl chlorination
Phosphine (1c) is heated to reflux 24h with 60mmol metallic sodiums in tetrahydrofuran solution, obtains the sodium salt (1d) of diethyl phosphine.Will
30mmol chloros ND sodium salt 1b is added in freshly prepared diethyl phosphine sodium (1d) solution, is heated to reflux 24h, by coupling
Reaction obtains the ND (1e) of diethyl phosphine substitution.After reaction terminates, the m-chloro-benzoic acid peroxide (mCPBA) of equivalent is added,
1h is stirred, it is rear to use hydrochloric acid conditioning solution pH to 7-8, the product after being aoxidized.Product is purified by vacuum sublimation, then uses second
Alcohol is recrystallized, and vacuum drying can obtain ligand 1 f white powder 1.13g, yield 15%.
1H NMR (400MHz, MeOD) δ 8.19-8.07 (m, 2H), 8.01 (d, J=7.2Hz, 1H), 6.51 (d, J=
7.2Hz, 1H), 2.10-1.90 (m, 4H), 1.02-0.90 (m, 6H).Mass spectral analysis (m/z, ESI)：Calculated value 250.1, experiment
Value 251.1 (M+H)+.Elementary analysis (weight/mass percentage composition %)：C, 57.64 (57.60)；H, 6.10 (6.04)；N, 11.16
(11.19) it is, theoretical value in bracket.
1.2 complex Eu1 synthesis
3mmol ligand 1 f and 3mmol NaOH are heated to reflux in the mixed solution of methanol and water 1: 1 (volume ratio)
30 minutes.Then the aqueous solution of the trichloride hydrate europiums of 1mmol six is added drop-wise in above-mentioned solution or suspension, flowed back 2 hours.Through
Filtering, washing, a small amount of methanol is washed, and is dried in vacuo.By recrystallizing methanol, white object europium complex 0.74g, yield are obtained
82%.Mass spectral analysis (m/z, ESI)：Calculated value 900.1, experiment value 901.1 (M+H)+.(quality percentage contains for elementary analysis
Measure %)：C, 47.80 (47.69)；H, 4.92 (4.87)；It is Eu10.5CH in N, 9.06 (9.14), bracket3OH·0.2H2O is managed
By value.
Embodiment 2.
The synthetic route being related in the present embodiment is as follows：
2.1 part 2f (3- methyl _ 4- hydroxyl -6- diethyl phosphine Oxy-1s, 5- naphthyridines, 3-methyl-4-hydroxy-6-
(diethylphosphoryl) synthesis -1,5-naphthyridine)
Synthesis step be the same as Example 1 (1.1 part), is simply changed to 3- methyl 4- by chloro- 1, the 5- naphthyridines (1a) of 4- hydroxyls -6-
Chloro- 1, the 5- naphthyridines (2a) of hydroxyl -6-.Obtain part 2f white powder 0.95g, yield 12%.
1H NMR (400MHz, MeOD) δ 8.15-8.03 (m, 2H), 7.99 (s, 1H), 2.68 (s, 3H), 2.11-1.92
(m, 4H), 1.03-0.90 (m, 6H).Mass spectral analysis (m/z, ESI)：Calculated value 264.1, experiment value 265.1 (M+H)+.Element point
Analyse (weight/mass percentage composition %)：C, 59.02 (59.09)；H, 6.48 (6.48)；It is theoretical value in N, 10.65 (10.60), bracket.
2.2 complex Eu2 synthesis
Synthesis step be the same as Example 1 (1.2 part), is simply changed to 2f by ligand 1 f.Obtain white object europium complex
0.73g, yield 78%.Mass spectral analysis (m/z, ESI)：Calculated value 942.1, experiment value 943.1 (M+H)+.Elementary analysis (quality
Percentage composition %)：C, 49.48 (49.62)；H, 5.33 (5.21)；It is Eu20.3CH in N, 8.78 (8.83), bracket3OH is managed
By value.
Embodiment 3.
The synthetic route being related in the present embodiment is as follows：
3.1 part 3f (3- cyano group -4- hydroxyl -6- diethyl phosphine Oxy-1s, 5- naphthyridines, 3-cyano-4-hydroxy-6-
(diethylphosphoryl) synthesis -1,5-naphthyridine)
Synthesis step be the same as Example 1 (1.1 part), is simply changed to 3- cyano group 4- by chloro- 1, the 5- naphthyridines (1a) of 4- hydroxyls -6-
Chloro- 1, the 5- naphthyridines (3a) of hydroxyl -6-.Obtain part 3f white powder 1.56g, yield 19%.
1H NMR (400MHz, MeOD) δ 8.36-8.20 (m, 2H), 8.16 (s, 1H), 2.18-1.96 (m, 4H), 1.03-
0.92 (m, 6H).Mass spectral analysis (m/z, ESI)：Calculated value 275.1, experiment value 276.1 (M+H)+.Elementary analysis (quality percentage
Content %)：C, 56.78 (56.73)；H, 5.09 (5.13)；It is theoretical value in N, 15.31 (15.27), bracket.
3.2 complex Eu3 synthesis
Synthesis step be the same as Example 1 (1.2 part), is simply changed to 3f by ligand 1 f.Obtain white object europium complex
0.83g, yield 85%.Mass spectral analysis (m/z, ESI)：Calculated value 975.1, experiment value 976.1 (M+H)+.Elementary analysis (quality
Percentage composition %)：C, 47.68 (47.89)；H, 4.33 (4.17)；It is Eu30.5CH in N, 12.67 (12.72), bracket3OH
Theoretical value.
Embodiment 4.
The synthetic route being related in the present embodiment is as follows：
4.1 part 4f (4- hydroxyl -6- di-t-butyl phosphine Oxy-1s, 5- naphthyridines, 4-hydroxy-6- (di-tert-
Butylphosphoryl synthesis) -1,5-naphthyridine)
Synthesis step be the same as Example 1 (1.1 part), is simply changed to di-t-butylchlorophosphine by diethyl phosphonium chloride (1c)
(4c).Obtain part 4f white powder 1.28g, yield 14%.Mass spectral analysis (m/z, ESI)：Calculated value 306.1, experiment value
307.1(M+H)+.Elementary analysis (weight/mass percentage composition %)：C, 62.74 (62.73)；H, 7.51 (7.57)；N, 9.14
(9.14) it is, theoretical value in bracket.
4.2 complex Eu4 synthesis
Synthesis step be the same as Example 1 (1.2 part), is simply changed to 4f by ligand 1 f.Obtain white object europium complex
0.82g, yield 77%.Mass spectral analysis (m/z, ESI)：Calculated value 1068.3, experiment value 1069.3 (M+H)+.Elementary analysis (matter
Measure percentage composition %)：C, 53.70 (53.53)；H, 6.51 (6.27)；It is Eu40.5H in N, 7.69 (7.80), bracket2O is managed
By value.
Embodiment 5.
The synthetic route being related in the present embodiment is as follows：
5.1 part 5f (4- hydroxyl -6- diphenylphosphine Oxy-1s, 5- naphthyridines, 4-hydroxy-6-
(diphenylphosphoryl) synthesis -1,5-naphthyridine)
Synthesis step be the same as Example 1 (1.1 part), is simply changed to diphenyl phosphine chloride by diethyl phosphonium chloride (1c)
(5c).Obtain part 5f white powder 1.98g, yield 19%.
1H NMR (400MHz, MeOD) δ 8.43 (d, J=4.4Hz, 1H), 8.22 (dd, J=8.6,3.0Hz, 1H), 8.05
(d, J=7.4Hz, 1H), 7.99 (dd, J=21.8,13.8Hz, 4H), 7.61-7.53 (m, 2H), 7.54-7.44 (m, 4H),
6.54 (d, J=7.2Hz, 1H).Mass spectral analysis (m/z, ESI)：Calculated value 346.1, experiment value 347.1 (M+H)+.Elementary analysis
(weight/mass percentage composition %)：C, 69.31 (69.36)；H, 4.38 (4.37)；It is theoretical value in N, 8.10 (8.09), bracket.
5.2 complex Eu5 synthesis
Synthesis step be the same as Example 1 (1.2 part), is simply changed to 5f by ligand 1 f.Obtain white object europium complex
0.97g, yield 82%.Mass spectral analysis (m/z, ESI)：Calculated value 1188.2, experiment value 1189.2 (M+H)+.Elementary analysis (matter
Measure percentage composition %)：C, 60.10 (60.12)；H, 3.74 (3.73)；It is Eu5 in N, 6.90 (6.94), bracket
0.6CH3OH·0.2H2O theoretical values.
Embodiment 6.
The synthetic route being related in the present embodiment is as follows：
6.1 part 6f (3- cyano group -4- hydroxyl -6- n-octyl sulphoxide base -1,5- naphthyridines, 3-cyano-4-hydroxy-6-
(octylsulfiyl) synthesis -1,5-naphthyridine)
Chloro- 1, the 5- naphthyridines (3a) of 3- cyano group -4- hydroxyls -6- and NaOH reactions are obtained into its sodium salt 3b.By the pungent of 10mmol
Mercaptan (6c) is heated to reflux 24h with 10mmol metallic sodiums in tetrahydrofuran solution, obtains spicy thioalcohol sodium (6d).By 10mmol chlorine
It is added to for ND sodium salt 3b in freshly prepared spicy thioalcohol sodium (6d) solution, is heated to reflux 24h, sulphur is obtained by coupling reaction
Ether (6e).Reaction terminate after, add equivalent m-chloro-benzoic acid peroxide (mCPBA), stir 1h, after use hydrochloric acid conditioning solution
PH to 7-8, the product after being aoxidized.By column chromatography for separation, (eluant, eluent is dichloromethane: methanol=10: 1), ethanol is tied again
Crystalline substance, obtains part 6f white powder 1.80g, yield 55%.
1H NMR (400MHz, DMSO) δ 8.82 (s, 1H), 8.28 (d, J=8.6Hz, 1H), 8.15 (d, J=8.6Hz,
1H), 3.19-3.09 (m, 1H), 3.02-2.90 (m, 1H), 1.73-1.63 (m, 1H), 1.39-1.28 (m, 3H), 1.26-1.10
(m, 8H), 0.84 (t, J=6.9Hz, 3H).Mass spectral analysis (m/z, ESI)：Calculated value 331.1, experiment value 332.1 (M+H)+.Member
Element analysis (weight/mass percentage composition %)：C, 61.60 (61.61)；H, 6.40 (6.39)；It is reason in N, 12.66 (12.68), bracket
By value.
6.2 complex Eu6 synthesis
3mmol part 6f and 3mmol NaOH are heated to reflux in the mixed solution of methanol and water 1: 1 (volume ratio)
30 minutes.Then the aqueous solution of the trichloride hydrate europiums of 1mmol six is added drop-wise in above-mentioned solution or suspension, flowed back 2 hours.Through
Filtering, washing, a small amount of methanol is washed, and is dried in vacuo.Obtain white object europium complex 0.91g, yield 80%.Mass spectral analysis
(m/z, ESI)：Calculated value 1143.3, experiment value 1144.3 (M+H)+.Elementary analysis (weight/mass percentage composition %)：C, 53.00
(53.07)；H, 5.43 (5.44)；It is Eu60.6CH in N, 10.77 (10.79), bracket3OH·0.3H2O theoretical values.
Embodiment 7.
The synthetic route being related in the present embodiment is as follows：
7.1 part 7 (3- cyano group -4- hydroxyl -6- n-octyl sulfuryl -1,5- naphthyridines, 3-cyano-4-hydroxy-6-
(octylsulfonyl) synthesis -1,5-naphthyridine)
M-chloro-benzoic acid peroxide (mCPBA) methanol solution of equivalent is added dropwise in 5mmol parts 6f, 1h is stirred.Through
Cross column chromatography for separation (eluant, eluent is dichloromethane: methanol=10: 1), recrystallizing methanol, it is white that vacuum drying can obtain part 7
Color powder 1.07g, yield 61%.
1H NMR (400MHz, DMSO) δ 13.03 (s, 1H), 8.81 (s, 1H), 8.34-8.28 (m, 2H), 3.58-3.43
(m, 2H), 1.69-1.48 (m, 2H), 1.42-1.27 (m, 2H), 1.27-1.14 (m, 8H), 0.83 (t, J=6.9Hz, 3H).Matter
Analysis of spectrum (m/z, ESI)：Calculated value 347.1, experiment value 348.1 (M+H).Elementary analysis (weight/mass percentage composition %)：C, 58.77
(58.77)；H, 6.08 (6.09)；It is theoretical value in N, 12.05 (12.09), bracket.
7.2 complex Eu7 synthesis
Synthesis step be the same as Example 6 (6.2 part), is simply changed to 7 by part 6f.Obtain light yellow target europium complex
1.04g, yield 88%.Mass spectral analysis (m/z, ESI)：Calculated value 1191.3, experiment value 1192.3 (M+H)+.Elementary analysis (matter
Measure percentage composition %)：C, 51.18 (51.19)；H, 5.20 (5.10)；It is Eu70.3H in N, 10.50 (10.53), bracket2O
By value.
Embodiment 8.
The synthetic route being related in the present embodiment is as follows：
8.1 part 8f (3- cyano group -4- hydroxyl -6- p-methylphenyl sulfoxide group -1,5- naphthyridines, 3-cyano-4-hydroxy-
6- (p-tolylsulfinyl) -1,5-naphthyridine) synthesis
Synthesis step be the same as Example 6 (6.1 part), is simply changed to toluene-ω-thiol (8c) by spicy thioalcohol (6c).Matched somebody with somebody
Body 8f white powder 1.98g, yield 51%.
Mass spectral analysis (m/z, ESI)：Calculated value 309.1, experiment value 310.1 (M+H)+.(quality percentage contains for elementary analysis
Measure %)：C, 62.09 (62.12)；H, 3.61 (3.58)；It is theoretical value in N, 13.57 (13.58), bracket.
8.2 complex Eu8 synthesis
Synthesis step be the same as Example 6 (6.2 part), is simply changed to 8f by part 6f.Obtain white object europium complex
0.88g, yield 82%.Mass spectral analysis (m/z, ESI)：Calculated value 1077.1, experiment value 1078.1 (M+H)+.Elementary analysis (matter
Measure percentage composition %)：C, 53.11 (53.03)；H, 3.01 (2.99)；It is Eu8 in N, 11.37 (11.48), bracket
0.5CH3OH·0.3H2O opinion values.
Embodiment 9.
The synthetic route being related in the present embodiment is as follows：
(3- cyano group -4- hydroxyl -6- are to methyl sulfuryl -1,5- naphthyridines, 3-cyano-4-hydroxy-6- (p- for 9.1 parts 9
Tolylsulfonyl synthesis) -1,5-naphthyridine)
Synthesis step be the same as Example 7 (7.1 part), is simply changed to 8f by 6f.Obtain the white powder 1.04g of part 9, yield
64%.Mass spectral analysis (m/z, ESI)：Calculated value 325.1, experiment value 326.1 (M+H)+.(quality percentage contains for elementary analysis
Measure %)：C, 59.09 (59.07)；H, 3.39 (3.41)；It is theoretical value in N, 12.91 (12.92), bracket.
9.2 complex Eu9 synthesis
Synthesis step be the same as Example 6 (6.2 part), is simply changed to 9 by part 6f.Obtain white object europium complex
0.96g, yield 86%.Mass spectral analysis (m/z, ESI)：Calculated value 1125.1, experiment value 1126.1 (M+H)+.Elementary analysis (matter
Measure percentage composition %)：C, 51.18 (51.08)；H, 2.69 (2.72)；It is Eu90.2H in N, 11.20 (11.17), bracket2O
By value.
Rare earth compounding shown in the synthesis type VV of comparative example 1.
By 3mmol 8mCND, (i.e. 3- cyano group -4- hydroxyls -8- methyl isophthalic acids, 5- naphthyridines, synthetic method is referring to patent of invention
CN201110139842.1) NaOH with 3mmol is heated to reflux 30 points in the mixed solution of ethanol and water 1: 1 (volume ratio)
The aqueous solution of the trichloride hydrate europiums of 1mmol six, is then added drop-wise in above-mentioned solution or suspension by clock, flows back 2 hours.By
Filter, washing, a small amount of ethanol is washed, and is dried in vacuo, is obtained complex Eu (8mCND)3(H2O)2.Then it will be obtained in acetone soln
Complex and 2mmol triphenylphosphine oxides (TPPO) be mixed and heated backflow 1 hour.Solvent evaporated, you can obtain target europium
Complex micro-yellow powder 1.13g.Mass spectrum (ESI-MS) is analyzed, and measures molecular ion peak M/Z=1262.3, [M+H]+。
Rare earth compounding shown in the synthesis type VVI of comparative example 2.
By 4mmol TTA (i.e. 2- TTAs, 0.89g) and 4mmol NaOH (0.16g) ethanol with
It is heated to reflux 30 minutes in the mixed solution of water 1: 1 (volume ratio, 50mL).Then by the trichloride hydrate europiums (0.37g) of 1mmol six
The aqueous solution be added drop-wise in above-mentioned solution or suspension, flow back 2 hours.By filtering, washing, a small amount of ethanol is washed, and is dried in vacuo.
Then recrystallized with ethanol/chlorobenzene, obtain buff powder 1.05g.Mass spectrum (ESI-MS) is analyzed, and measures molecular ion peak M/Z
=1036.9, [M-Na].
<The property representation of complex>
The luminosity of embodiment 10., heat endurance, the sign of photostability
The present invention technique effect mainly by the emission spectrum of the rare earth compounding in embodiment, photoluminescence quantum yield,
Heat endurance and ultraviolet tolerance embody.Wherein, photoluminescence quantum yield is tested using integrating sphere, and heat endurance passes through N2
The thermogravimetric analysis heat decomposition temperature that draws of test is carried out under atmosphere to weigh, and ultraviolet tolerance is by testing rare earth compounding
Luminous intensity attenuation of the macromolecule membrane (PMMA) of doping under ultraviolet light is weighed.Quantum yield is in France
Tested on the Nanolog FL3-2iHR type infrared spectrometers of HORIBA JOBIN companies production.Thermogravimetric analysis is in U.S. TA
Tested on the Q600SDT spectrometers of company's production.Ultraviolet ageing is UVA340 type fluorescent tubes, and power is 40 watts, spoke during test
It is 25~30 watts/square meter according to intensity.
The test result of representational several complexs is only listed, as shown in table 1.
First, the europium complex obtained by the present invention can see bright-coloured, bright feux rouges under the exciting of ultraviolet light.Match somebody with somebody
Ultraviolet-visible absorption spectroscopies of the compound Eu3 in dichloromethane solution is as shown in figure 1, its solid powder is excited and emission spectrum
As shown in Figure 2.The quantum yield of solid powder is up to 94%, compared with europium complex reported in the literature in highest level it
Row.Exciting for other complexs is similar with emission spectrum with Eu3, it may have good luminous quantum efficiency.Show this kind of cooperation
Thing is potential to be used as efficient down-conversion luminescent material.
Secondly, the europium complex obtained by the present invention has enough heat endurances.Complex Eu5 heat decomposition temperature is high
Up to 440 degrees Celsius, show this kind of compound not only structural rigidity, and do not use neutral ligand, it is easy in the absence of neutral ligand
The technical problem of dissociation.As control, the heat decomposition temperature of the complex in comparative example 1 is only 230 degrees Celsius, is shown in heating
Under the conditions of be easy to the dissociation that occurs neutral ligand TPPO.
Again, the europium complex obtained by the present invention has enough photostability.Complex is ultraviolet in 40W UVA340
Irradiated 20 hours under fluorescent tube, obvious light degradation is not observed.As control, the beta-diketon class rare earth compounding in comparative example 2
[Eu (TTA) 4] Na (TTA be 2- TTAs), by being irradiated 20 hours under ultraviolet lamp tube, luminous intensity pole
It is big to weaken.
In addition, the europium complex obtained by the present invention also has high ligand stability constant, by consolidating for this kind of europium complex
Body powder is placed in strong acid or strong base solution to be soaked all without the disappearance for causing luminescent properties for a long time.
Table 1
a：Represent that solid powder sample measures to obtain result in integrating sphere.b：Test result of the ultraviolet irradiation after 20 hours.
c：Do not test.
<The application of rare earth compounding>
Complex Eu3 is dispersed in macromolecule PMMA by embodiment 11. is used as luminescent film
Rare earth compounding Eu3 and macromolecule PMMA resins are mixed with mass ratio 1: 100, and it is molten to be dissolved in dichloromethane
In liquid.Then obtained mixed liquor is formed into uniform polymeric membrane by way of spin coating in the Quartz glass surfaces of cleaning.
Resulting film is under the irradiation of uviol lamp, and naked eyes are visible can to send bright feux rouges.Surveyed using integrating sphere
92% can be reached by obtaining the absolute quantum yield of luminescence generated by light, be a kind of efficient light conversion film material.
The complex Eu3 of embodiment 12. is used as the luminescent material in electroluminescent device
The Rare Earth Europium Complex EL device structure of the present embodiment can be expressed as ITO/MoO3/TCTA(40nm)/
Eu3: BCPO (1: 15,20nm)/TmPyPB (40nm)/LiF/Al, wherein ITO represent indium tin oxide-coated glass, MoO3Represent
Molybdenum trioxide, LiF represents lithium fluoride, and Al represents metal aluminium electrode.The structural formula of used other materials is shown in Fig. 3.
Electroluminescent device can be made by methods known in the art, such as press bibliography
Method disclosed in (Appl.Phys.Lett.1987,51,913) makes.Specific method is：(it is less than 8 × 10 in high vacuum-5Pa)
Under the conditions of, it is sequentially depositing hole mobile material, luminescent material, electric transmission on electro-conductive glass (ITO) substrate through over cleaning
Material and metallic cathode material.The thickness of each layer is monitored with quartz oscillator.
During measurement device performance, ITO electrode is connected with positive pole, and metal electrode is connected with negative pole, and a constant pressure is applied to device
While (generally between 3-30 volts), its voltage-to-current (I-V) curve and voltage-brightness (L-V) curve etc. are recorded.It is above-mentioned
Measurement is the combined system (see Fig. 4) for measuring of the analyzers of the Keithley 2400 and PR650 spectrometers controlled by computer.
Device is in 100cdm-2When emission spectrum it is as shown in Figure 5.
PRELIMINARY RESULTS shows that the electroluminescent device high-high brightness is up to 1180cdm-2, maximum current efficiency is 14cdA-1.In 100cdm-2When, current efficiency is 2.7cd A-1.With the disclosed electroluminescent based on europium complex in document
Device is compared, and the performance of heretofore described electroluminescent device is in higher level.Believe by optimization, based on this kind of europium
The efficiency of the electroluminescent device of complex still has the space of lifting.
Claims (12)
1. a kind of europium complex, its general structure is Eu (t-ND)3, wherein t-ND is the later phosphine epoxide of deprotonation, sulfoxide group
Or 4- hydroxyl -1,5- naphthyridine type anion ligands of sulfuryl substitution；The structure of the europium complex such as formula IV, Formula V and Formula IV institute
Show：
Wherein, R1、R2、R3、R4Each stand alone as hydrogen atom, halogen atom, cyano group, C1-C8 straight or branched alkyl, C1-C8
Straight or branched halogen-substituted alkyl；R5For C1-C18 straight or branched alkyl, phenyl, naphthyl or substituted phenyl,
Described substituted phenyl be by halogen atom, methyl, ethyl, isopropyl, the tert-butyl group, methoxyl group, ethyoxyl, trifluoromethyl,
The phenyl that dimethylamino is replaced.
2. europium complex as claimed in claim 1, it is characterised in that R5For methyl, ethyl, n-propyl, isopropyl, normal-butyl,
The tert-butyl group, n-octyl, dodecyl, n-hexadecyl, n-octadecane base, phenyl, naphthyl, 2- fluorophenyls, 2- chlorphenyls, 2-
Bromophenyl, 3- fluorophenyls, 3- chlorphenyls, 3- bromophenyls, 4- fluorophenyls, 4- chlorphenyls, 4- bromophenyls, 2,3- dichlorophenyls, 2,
4- dichlorophenyls, 2,5- dichlorophenyls, 2,6- dichlorophenyls, 3,4- dichlorophenyls, 3,5- dichlorophenyls, 2- aminomethyl phenyls, 2-
Ethylphenyl, 2- isopropyl phenyls, 2- tert-butyl-phenyls, 4- aminomethyl phenyls, 4- ethylphenyls, 4- isopropyl phenyls, the tertiary fourths of 4-
Base phenyl, 2,4- 3,5-dimethylphenyls, 2,5- 3,5-dimethylphenyls, 2,6- 3,5-dimethylphenyls, 3,5- 3,5-dimethylphenyls, 2- methyl -5-
Tert-butyl-phenyl, 2- methoxyphenyls, 3- methoxyphenyls, 4- methoxyphenyls, 2- dimethylamino phenyls, 4- Dimethylaminobenzenes
Base.
3. europium complex as claimed in claim 1, it is characterised in that R5For methyl, ethyl, n-propyl, isopropyl, normal-butyl,
The tert-butyl group, n-octyl, dodecyl, n-hexadecyl, n-octadecane base, phenyl, naphthyl, p-methylphenyl.
4. europium complex as claimed in claim 1, it is characterised in that R1、R2、R3、R4Each stand alone as hydrogen atom, cyano group, first
Base；R5For ethyl, the tert-butyl group, n-octyl, phenyl, p-methylphenyl.
5. the tooth anion ligand of 4- hydroxyls -1,5- naphthyridine type three of a kind of phosphine epoxide, sulfoxide group or sulfuryl substitution, its structure such as formula
Shown in I, Formula II and formula III：
Wherein, R1、R2、R3、R4Each stand alone as hydrogen atom, halogen atom, cyano group, C1-C8 straight or branched alkyl, C1-C8
Straight or branched halogen-substituted alkyl；R5For C1-C18 straight or branched alkyl, phenyl, naphthyl or substituted phenyl,
Described substituted phenyl be by halogen atom, methyl, ethyl, isopropyl, the tert-butyl group, methoxyl group, ethyoxyl, trifluoromethyl,
The phenyl that dimethylamino is replaced.
6. anion ligand as claimed in claim 5, it is characterised in that R1、R2、R3、R4Each stand alone as hydrogen atom, cyano group,
Methyl；R5For ethyl, the tert-butyl group, n-octyl, phenyl, p-methylphenyl.
7. the preparation method of the europium complex in Claims 1 to 4 described in any one, cloudy using three teeth shown in Formulas I-III
Ion ligand, alkali and rare earth salts react in a solvent, and the europium complex shown in formula IV-VI is made：
Wherein, the alkali is selected from hydroxide, carbonate, ammoniacal liquor, organic amine；The rare earth salts are selected from hydrochloride, the nitre of europium
Hydrochlorate, acetate or trifluoro sulfonate；In Formulas I-VI, R1、R2、R3、R4And R5Scope with described in claim 1-4.
8. preparation method as claimed in claim 7, it is characterised in that three tooth anion ligands, alkali shown in the Formulas I-III
It is 3: 3: 1 with the mol ratio that rare earth salts react；One or more mixtures of the solvent in following solvent：Water,
Ethanol, methanol, isopropanol, acetone, tetrahydrofuran, acetonitrile, toluene, dichloromethane, chloroform, ether, N, N- dimethyl methyls
Acid amides；The temperature of reaction is -10~120 DEG C, and the time is 10 minutes~24 hours.
9. the preparation method of three tooth anion ligands described in claim 5, using the 4- hydroxyls of the 6- positions halogen substitution shown in Formula VII
Base -1,5- naphthyridine type part and the organic chloride phosphine shown in Formula VIII or the thiol reactant shown in Formula IV V, it is even by the first step
Connection reaction, second step oxidation reaction is obtained：
In Formula VII, X represents halogen atom, R1、R2、R3、R4Scope with described in claim 5；In Formula VIII and Formula IV V, R5's
Scope is with described in claim 5.
10. preparation method as claimed in claim 9, it is characterised in that first, 4- hydroxyl -1,5- naphthalenes of 6- halogen substitutions
Pyridine class part captures proton with alkali reaction, and organic chloride phosphine or mercaptan obtain corresponding salt, Ran Houjin with alkali metal reaction
Row coupling reaction；Next, adding oxidant carries out oxidation reaction, the oxidant is selected from oxygen, ozone, chlorine, chlorine water, secondary
Sodium chlorate, perbenzoic acid, m-chloro-benzoic acid peroxide, Peracetic acid, hydrogen peroxide；Eventually pass appropriate post processing and carry
It is pure to obtain product.
11. europium complex in Claims 1 to 4 described in any one is used as the application of luminescent material.
12. application as claimed in claim 11, it is characterised in that the rare earth compounding shines through ultraviolet source or royal purple light source
Penetrate and light, or the rare earth compounding is excited and lighted by electric energy.
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