CN101792508B - Unconjugated organic phosphorus, oxide and rare earth coordination polymer as well as preparation method and application thereof - Google Patents

Unconjugated organic phosphorus, oxide and rare earth coordination polymer as well as preparation method and application thereof Download PDF

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CN101792508B
CN101792508B CN2010101089353A CN201010108935A CN101792508B CN 101792508 B CN101792508 B CN 101792508B CN 2010101089353 A CN2010101089353 A CN 2010101089353A CN 201010108935 A CN201010108935 A CN 201010108935A CN 101792508 B CN101792508 B CN 101792508B
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phosphine oxygen
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许辉
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Heilongjiang University
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Abstract

The invention provides an unconjugated organic phosphorus, oxide and rare earth coordination polymer as well as a preparation method and application thereof, which relate to an organic phosphorus, oxide and rare earth coordination polymer as well as a preparation method and application thereof and solve the problems that the traditional rare earth electroluminescent coordination polymer has large preparation difficult, long cycle, unstable quality and property, low brightness and efficiency, and the like. The polymer has the structural formula that the polymer can be prepared by using a polymerizable organic phosphorus, oxide and rare earth compound and vinyl carbazole as monomers and copolymerizing by free radicals; the polymerizable organic phosphorus, oxide and rare earth compound monomer is prepared from a polymerizable organic phosphorus and oxide compound neutral ligand, a beta-diketone anion ligand and rare earth center metal ions through matching reaction. The polymer is used for the luminescent layer material or the luminescent layer doping material of an electroluminescent device. The light starting voltage of the manufactured electroluminescent device is 12.5-21V, and the electroluminescent brightness is 15-150cd/m<2>. The polymer can be used as an electric active layer of a polymer electric storing device. The cycle of the method is short.

Description

The unconjugated organic phosphorus, oxide rare earth coordination polymer
Technical field
The present invention relates to a kind of organophosphorus oxygen rare earth coordination polymer.
Background technology
Be that the organic electronic of research object is learned and to have been obtained flourishly with organic materials and device since the eighties in last century, comprising photoelectric information functional material, organic photoconductive, organic laser material, having numerous areas such as dynamo-electric stable state material and organic solar batteries to obtain the achievement that attracts people's attention.REE just shines flourishing vitality as the important element in the inorganic semiconductor once introducing organic electronic field, all shows outstanding characteristics and wide application prospect in every field.
Rare earth electroluminescent title complex is because its illuminant colour purity high (peak width at half is less than 10 nanometers), and stability is strong and high to 100% theoretical internal quantum efficiency, is the organic electroluminescent hot research fields always.In recent years, along with solution processing technology manifests in the advantage aspect the device moulding day by day, the rare earth coordination polymer with solution processable characteristic more and more receives publicity.
Though small molecules rare earth electroluminescent title complex has good luminous property, because their exciton life-span is longer, generally exist serious concentration quenching and triplet state to bury in oblivion phenomenon, so its device is main with doping and blend device.Its way is to select a kind of material of main part with suitable excited level, forms the luminescent layer of electroluminescent device by a certain percentage with rare earth compounding.Because doping and blend are physics dispersion processes; Situation such as in the device working process, might be separated, therefore material of main part and rare earth compounding being combined with the form of chemical bond becomes the importance that the electroluminescent rare earth compounding is studied.PVK (PVK) is one type of common material of main part; It has good photoelectric characteristic and higher excited level; Therefore, reaction realizes that the Subjective and Objective of multipolymer is integrated and becomes a kind of feasible method as copolymerization units and polymerizable rare earth compounding with VCz.But the rare earth electroluminescent ligand polymer that exploitation is at present used all exists brightness and the general shortcoming on the low side of efficient.Major cause is to have certain defective on the employed polymerizable rare earth compounding structure.On the one hand; For molecular weight and the stability of rare earth compounding monomer in polymerization process that improves polymkeric substance; The work that part has been reported uses acrylic acid or the like anion ligand and rare earth ion to form the polymerizable title complex; But, therefore compare with two ketone parts and have tangible inferior position at aspects such as the sensitization of rare earth ion and the transmission of polymer molecule self-energy because vinylformic acid do not possess photoelectric activity; On the other hand, the neutral ligand that is widely used in the electroluminescent rare earth compounding now is 1,10-o-phenanthroline nitrogen heterocycles verivates such as (phen).This type of neutral ligand has good carrier transport ability, but the co-ordination bond that nitrogen-atoms and rare earth ion form a little less than, simultaneously, 1, the condition of 10-o-phenanthroline analog derivative functionalization is higher.In order to prevent that functional modification from causing coordination ability to descend, require between cavity transmission group and o-phenanthroline, to add part buffering group, be generally big steric group or long carbochain.Do like this and not only prolonged reactions step, improved cost, and bigger steric effect will hinder the chainpropagation in the polymerization process, and reduce the stability of title complex in polymerization process.
Summary of the invention
The purpose of this invention is to provide a kind of unconjugated organic phosphorus, oxide rare earth coordination polymer, solved that existing rare earth electroluminescent ligand polymer exists that the preparation difficulty is big, preparation cycle long, quality and unstable properties, brightness and efficient problem of lower.
Unconjugated organic phosphorus, oxide rare earth coordination polymer of the present invention be with polymerizable organic phosphine oxygen rare earth compounding and VCz as monomer, obtain through free-radical polymerized, unconjugated organic phosphorus, oxide rare earth coordination polymer chemical structural formula is shown in (I):
Figure GSA00000027147400021
Wherein, n: m=1: 99～10: 90, m+n=100, m, n are positive integer.
N is the monomeric number of repeat unit of polymerizable organic phosphine oxygen rare earth compounding in the unconjugated organic phosphorus, oxide rare earth coordination polymer of the present invention, and m is the number of repeat unit of VCz.
Polymerizable organic phosphine oxygen rare earth compounding monomer in the unconjugated organic phosphorus, oxide rare earth coordination polymer of the present invention is to be obtained by polymerizable organic phosphine oxygen compound neutral ligand, beta-diketon anion ligand and rare earth central metallic ions complex reaction, and the chemical structural formula of polymerizable organic phosphine oxygen rare earth compounding is suc as formula shown in (II):
Wherein, RE is a REE; R 1For containing the group of alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon; R 2For containing the group of alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon; R 3For containing the group of alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon.
The chemical structural formula of polymerizable organic phosphine oxygen compound neutral ligand is shown in (III) in the polymerizable organic phosphine oxygen rare earth compounding monomer of the present invention:
Figure GSA00000027147400032
Wherein, Ar is the group with cavity transmission ability, for aromatic hydrocarbons, contain heteroatomic aromatic hydrocarbons or contain the arene derivatives of alkyl, alkoxyl group, aryl or aromatic amine groups.
The chemical structural formula of beta-diketon anion ligand is shown in (IV) in the polymerizable organic phosphine oxygen rare earth compounding monomer of the present invention:
Figure GSA00000027147400033
Wherein, R 1For containing the group of alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon; R 2For containing the group of alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon; R 3For containing the group of alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon.
The preparation method of unconjugated organic phosphorus, oxide rare earth coordination polymer of the present invention is: with polymerizable organic phosphine oxygen compound rare earth compounding and VCz is that 1: 1.3～100 ratio adds in the organic solvent in molar ratio; And then adding radical initiator; At inert gas atmosphere, 60～80 ℃ of following reaction 10～90h, behind sedimentation, separation, extraction, drying, desolventizing, promptly get the unconjugated organic phosphorus, oxide rare earth coordination polymer more then; Wherein organic solvent is THF or methylene dichloride; The ratio of VCz molar weight and organic solvent volume is 1mmol: 0.5～10mL; Radical initiator is azo class or peroxide initiator, and the molar weight of radical initiator is 5% of polymerizable organic phosphine oxygen compound rare earth compounding and a VCz integral molar quantity.
Radical initiator among the preparation method of unconjugated organic phosphorus, oxide rare earth coordination polymer of the present invention is Diisopropyl azodicarboxylate (AIBN), Lucidol etc.
The used rare earth compounding monomer of the preparation method of unconjugated organic phosphorus, oxide rare earth coordination polymer of the present invention does not have big steric group and coordination structure to stablize; Steric effect is little during with the VCz copolymerization, has improved polymkeric substance and the coordination compound monomer stability in polymerization process.Therefore, preparation method of the present invention is simple, and the cycle is short, and cost is low, constant product quality.
The preparation method of used polymerizable organic phosphine oxygen rare earth compounding is among the preparation method of unconjugated organic phosphorus, oxide rare earth coordination polymer of the present invention: three normal beta-diketons are dissolved in the organic solvent; Add the aqueous sodium hydroxide solution that contains three Equivalent Hydrogen sodium oxides again; Then behind reaction 15～30min under 60 ℃; Add again behind the rare earth soluble salt of monovalent at 60 ℃ of reaction 30～60min down, and then the polymerizable organic phosphine oxygen compound of monovalent is added in the previous reaction system, then 60～70 ℃ of reactions 2～8 hours down; Behind extraction, separation, drying, desolventizing, recrystallization gets polymerizable organic phosphine oxygen rare earth compounding more then; Wherein, the ratio of the molar weight of beta-diketon and organic solvent volume is 3mmol: 10mL, and organic solvent is alcohols, THF or methylene dichloride.
The preparation method of used polymerizable organic phosphine oxygen compound realizes through following steps among the preparation method of polymerizable organic phosphine oxygen rare earth compounding of the present invention: one, under room temperature, alkaline system; With purifying to such an extent that vinyl benzyl replaces the Ar bromide behind Ar bromide and the vinyl chloride hybrid reaction 12～18h, wherein the mol ratio of Ar bromide and vinyl chloride is 1: 1～1.5; Two, the vinyl benzyl that step 1 is obtained replaces the Ar bromide and adds in the organic solvent after anhydrous and oxygen-free is handled, and stirring and dissolving gets mixed system, then mixed system is cooled to-78～0 ℃; Insulation adds n-Butyl Lithium afterreaction 1～2h again in mixed system, react 0.5～1h again after being warming up to room temperature then; And then mixed system is cooled to-78～0 ℃, insulation is after diethyl ether solution or the volumetric concentration that adds volumetric concentration again and be 50% diphenyl phosphine chloride is the tetrahydrofuran solution of 50% diphenyl phosphine chloride; Reaction 1～3h; Be warming up to room temperature afterreaction 8～24h again, purify and obtain the organic phosphine oxygen compound, wherein; Organic solvent is anhydrous diethyl ether or THF; The mol ratio that vinyl benzyl replaces Ar bromide and n-Butyl Lithium is 1: 2～2.5, and the ratio that vinyl benzyl replaces Ar bromide and organic solvent is 1mmol: 5mL, and the mol ratio that vinyl benzyl replaces Ar bromide and diphenyl phosphine chloride ether is 1: 1; Three, the organic phosphine oxygen compound that step 2 is obtained adds in the organic solvent, and stirring and dissolving adds ydrogen peroxide 50 again; And then react 2～4h under the room temperature, obtain polymerizable organic phosphine oxygen compound, wherein; Organic solvent is 1; 4-dioxane, methylene dichloride, chloroform etc., the ratio of organic phosphine oxygen compound and organic solvent is 1mmol: 5mL, H in organic phosphine oxygen compound and the ydrogen peroxide 50 2O 2Mol ratio be 1: 1～1.5.
Preparing method's neutral and alkali system of polymerizable organic phosphine oxygen compound of the present invention is the mixed system of Tetrabutyl amonium bromide, DMSO 99.8MIN. (DMSO) and alkaline aqueous solution; The volume ratio of alkaline aqueous solution and DMSO 99.8MIN. is 1: 8～10; The ratio of Tetrabutyl amonium bromide quality and DMSO 99.8MIN. volume is 4～4.5g: 1L; The volumetric molar concentration of alkaline aqueous solution is 1～5mol/L, is potassium hydroxide solution, sodium hydroxide solution or solution of potassium carbonate.
Unconjugated organic phosphorus, oxide rare earth coordination polymer of the present invention is used for the application of the luminescent layer material or the luminescent layer dopant material of electroluminescent device.
Non-conjugated organic phosphine oxygen rare earth coordination polymer of the present invention is as the application of the electroactive layer of electrostrictive polymer memory device.
With respect to similar polymer rare earth photoelectricity functional material; Design synthetic unconjugated organic phosphorus, oxide rare earth coordination polymer has the characteristics of three aspects among the present invention: 1, the unconjugated organic phosphorus, oxide rare earth coordination polymer is the main repeating unit of backbone structure with the polyvinyl carbazole, guarantees that polymkeric substance has good current carrier and injects and transmittability; 2, through modifying the excited level that to regulate polymerizable organic phosphine oxygen compound part easily, make it to become the bridge of transmission ofenergy between polyvinyl carbazole main chain and the rare earth ion, thereby obtain higher luminous efficiency and brightness; 3, inject and transmittability through kind that changes functional group and the current carrier that proportioning can be regulated the organic phosphine oxygen compound effectively; Make organic phosphine oxygen rare earth compounding unit can have the effect of carrier traps or exciton trap, this effect can greatly promote polymer electroluminescence and electric memory property.
Organic phosphine oxygen compound of the present invention has outstanding characteristics on functional modification and molecular designing; Be in particular in three aspects: 1. the organic phosphine oxygen compound has a plurality of positions of modifying; Can realize multifunctional all easily, not influence its coordination ability simultaneously; 2. each phosphorus atom of organic phosphine oxygen compound links to each other with three aromatic groups through three carbon phosphorus singly-bounds, forms the two keys of phosphorus oxygen with a Sauerstoffatom again.Because single bonded spinability and bond angle can be adjusted, so the organic phosphine oxygen compound itself has the certain structure regulating power, can be in realization polyreaction under the exacting terms relatively; 3. the excited level of organic phosphine oxygen compound can be regulated through functionalized modification easily, and the excited level of itself and rare earth ion is complementary, and realizes intramolecular energy transfer efficiently, improves the luminous efficiency of material.Therefore the polymerizable organic phosphine oxygen compound neutral ligand that is adopted among the present invention is the key that realizes the non-conjugated rare earth coordination polymer of high-performance.
To sum up; With polymer phase ratio of the same type; The novel non-conjugated photoelectric functional rare earth coordination polymer that obtains through polymerizable organic phosphine oxygen rare earth compounding monomer and VCz copolymerization all has remarkable advantages on polymerization complexity, polymericular weight and MWD and each item photoelectric properties index; Inject aspects such as transmission, carrier capture and exciton formation at intramolecular energy transfer, current carrier and can greatly promote polymer properties, make this base polymer at organic electroluminescent, organic laser with there is organic electronic field such as dynamo-electric storage to have the application prospect of desirable.
Unconjugated organic phosphorus, oxide rare earth coordination polymer of the present invention is 12.5～21V as the bright voltage that opens of the electroluminescent device of the luminescent layer material of electroluminescent device or luminescent layer dopant material; Current density can reach 60～265mA/cm, and electroluminescent brightness can reach 15～150cd/m 2Polymer application of the present invention can reach 0.43% in the maximum external quantum efficiency of electroluminescent device.
Description of drawings
Fig. 1 is P1 in the practical implementation 19 1%The UVF spectrogram; Fig. 2 is the P1 of embodiment 20 3%The UVF spectrogram; Fig. 3 is P4 in the embodiment 28 1%The UVF spectrogram; Fig. 4 is P4 in the embodiment 29 3%The UVF spectrogram; Fig. 5 is the current-voltage-brightness curve figure of the electroluminescent device of embodiment 55; Fig. 6 is the electroluminescent spectrum figure of the electroluminescent device of embodiment 55; Fig. 7 is the current-voltage-brightness curve figure of the electroluminescent device of embodiment 56; Fig. 8 is the current-voltage-brightness curve figure of the electroluminescent device of embodiment 57; Fig. 9 is the electroluminescent spectrum figure of the electroluminescent device of embodiment 57; Figure 10 is the current-voltage-brightness curve figure of the electroluminescent device of embodiment 58; Wherein, curve 1 is the uv absorption spectrum curve among Fig. 1 to Fig. 4, and curve 2 is the photoluminescence curve of spectrum; "--zero--" is the voltage-to-current densimetric curve among Fig. 5, Fig. 7, Fig. 8 and Figure 10,
Figure GSA00000027147400071
Be voltage-brightness curve.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: this embodiment unconjugated organic phosphorus, oxide rare earth coordination polymer is as monomer with polymerizable organic phosphine oxygen rare earth compounding and VCz; Obtain through free-radical polymerized, unconjugated organic phosphorus, oxide rare earth coordination polymer chemical structural formula is shown in (I):
Figure GSA00000027147400072
Wherein, n: m=1: 99～10: 90, m+n=100, m, n are positive integer; RE is a REE; Ar is the group with cavity transmission ability, for aromatic hydrocarbons, contain heteroatomic aromatic hydrocarbons or contain the arene derivatives of alkyl, alkoxyl group, aryl or aromatic amine groups; R 1For containing the group of alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon; R 2For containing the group of alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon; R 3For containing the group of alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon.
N is the monomeric number of repeat unit of polymerizable organic phosphine oxygen rare earth compounding in this embodiment, and m is the number of repeat unit of VCz.
This embodiment polymer application can reach 0.43% in the maximum external quantum efficiency of electroluminescent device.
Embodiment two: that this embodiment and embodiment one are different is n: m=3: 97～6: 94.Other parameter is identical with embodiment one.
Embodiment three: that this embodiment and embodiment one are different is n: m=5: 95.Other parameter is identical with embodiment one.
Embodiment four: this embodiment and embodiment one, two or three are different is that polymerizable organic phosphine oxygen rare earth compounding monomer in the unconjugated organic phosphorus, oxide rare earth coordination polymer is to be obtained by polymerizable organic phosphine oxygen compound neutral ligand, beta-diketon anion ligand and rare earth central metallic ions complex reaction, and the chemical structural formula of polymerizable organic phosphine oxygen rare earth compounding is suc as formula shown in (II):
Figure GSA00000027147400081
other parameter is identical with embodiment one, two or three.
Embodiment five: what this embodiment and embodiment one to four were different is that RE is lanthanum, cerium, praseodymium, rubidium, promethium, samarium, europium, gadolinium, dysprosium, holmium, terbium, erbium, thulium, ytterbium or lutetium rare earth ion.Other parameter is identical with embodiment one to four.
Embodiment six: this embodiment and embodiment one to five are different be the chemical structural formula of polymerizable organic phosphine oxygen compound neutral ligand in the polymerizable organic phosphine oxygen rare earth compounding monomer shown in (III):
Figure GSA00000027147400082
other parameter is identical with embodiment one to five.
The polymerizable organic phosphine oxygen compound neutral ligand of this embodiment has a plurality of positions of modifying, and can realize multifunctional all easily, does not influence its coordination ability simultaneously; Each phosphorus atom links to each other with three aromatic groups through three carbon phosphorus singly-bounds, forms the two keys of phosphorus oxygen with a Sauerstoffatom again.Because single bonded spinability and bond angle can be adjusted, so the organic phosphine oxygen compound itself has the certain structure regulating power, can be in realization polyreaction under the exacting terms relatively; Excited level can be regulated through functionalized modification easily, and the excited level of itself and rare earth ion is complementary, and realizes intramolecular energy transfer efficiently, improves the luminous efficiency of material.Therefore the polymerizable organic phosphine oxygen compound neutral ligand of this embodiment is the key that realizes the non-conjugated rare earth coordination polymer of high-performance.
Embodiment seven: what this embodiment and embodiment one to six were different is that Ar is carbazole or di-p-methoxy-diphenylamine.Other parameter and embodiment one to six phase are together.
Embodiment eight: this embodiment and embodiment one to seven are different be the chemical structural formula of beta-diketon anion ligand in the polymerizable organic phosphine oxygen rare earth compounding monomer shown in (IV):
Wherein, R 1For containing the group of alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon; R 2For containing the group of alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon; R 3For containing the group of alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon.Other parameter is identical with embodiment one to seven.
Embodiment nine: what this embodiment and embodiment one to eight were different is that the R1 in the beta-diketon anion ligand is trifluoromethyl, perfluoro propyl or phenyl in the polymerizable organic phosphine oxygen rare earth compounding monomer; R2 is hydrogen, fluorine or bromine; R3 is phenyl, thienyl or naphthyl etc.Other parameter is identical with embodiment one to eight.
Beta-diketon is specially thienyl trifluoromethyl methyl ethyl diketone, phenylbenzene methyl ethyl diketone or methyl ethyl diketone in this embodiment.But be not limited to above several kinds, other beta-diketon commonly used of this area all can be used for this embodiment.
Embodiment ten: what this embodiment and embodiment six were different is that Ar is a carbazole; Phosphorus atom replaces in the contraposition of nitrogen-atoms; When phosphorus atom simultaneously forms the two key of phosphorus oxygen with Sauerstoffatom; Polymerizable organic phosphine oxygen compound neutral ligand is 3,6-diphenylphosphine oxo-N-(4-vinyl benzyl) carbazole, and its chemical structural formula is shown in (V):
Figure GSA00000027147400092
other parameter and embodiment six phase are together.
3 of this embodiment, the proton nmr spectra of 6-diphenylphosphine oxo-N-(4-vinyl benzyl) carbazole (400MHz, solvent are deuterochloroform, and confidential reference items are TMS): δ=7.669-7.775 (m; 12H), and 7.410-7.492 (m, 6H), 7.306-7.396 (m; 10H), 7.027 (d, J=8.0Hz; 2H), 6.690 (q, J 1=10.8Hz, J 2=17.6Hz, 1H), 5.714 (d, J=17.6Hz, 1H), 5.456 (s, 2H), 5.238ppm (d, J=10.8Hz, 1H).Flight time mass spectrum: m/z (%): 683 (100) [M +].
3 of this embodiment, near infrared spectrogram (pressing potassium bromide troche, the cm of 6-diphenylphosphine oxo-N-(4-vinyl benzyl) carbazole -1): 3076,2918,1630 (C=C stretching vibrations), 1482,1438 (C-P stretching vibrations), 1314,1264,1177 (P=O stretching vibrations), 1129,959,755,727,692,551,525,435.Ultimate analysis (quality %) theoretical value: C 79.05, H 5.16, and N 2.05, and O 4.68; Measured value: C79.39, H 5.07, and N 2.36, and O 4.80.
Embodiment 11: what this embodiment and embodiment six were different is that Ar is a carbazole; Phosphorus atom replaces on position between nitrogen-atoms; When phosphorus atom simultaneously forms the two key of phosphorus oxygen with Sauerstoffatom; Polymerizable organic phosphine oxygen compound neutral ligand is 2,7-diphenylphosphine oxo-N-(4-vinyl benzyl) carbazole, and its structural formula is shown in (VI):
Figure GSA00000027147400101
other parameter and embodiment six phase are together.
Embodiment 12: what this embodiment and embodiment six were different is that Ar is a di-p-methoxy-diphenylamine; Phosphorus atom replaces on the ortho position of nitrogen-atoms; When phosphorus atom simultaneously forms the two key of phosphorus oxygen with Sauerstoffatom; Polymerizable organic phosphine oxygen compound neutral ligand is 2,2 '-diphenylphosphine oxo-N-(4-vinyl benzyl) pentanoic, and its structural formula is shown in (VII):
Figure GSA00000027147400102
other parameter and embodiment six phase are together.
Embodiment 13: what this embodiment and embodiment one to nine were different is that Ar is a di-p-methoxy-diphenylamine; Phosphorus atom replaces on the ortho position of nitrogen-atoms; When phosphorus atom simultaneously formed the two key of phosphorus oxygen with Sauerstoffatom, polymerizable organic phosphine oxygen compound neutral ligand was 2,2 '-diphenylphosphine oxo-4; 4 '-dimethoxy-N-(4-vinyl benzyl) pentanoic, its structural formula is shown in (VIII):
Figure GSA00000027147400111
other parameter and embodiment six phase are together.
2 of this embodiment, 2 '-diphenylphosphine oxo-4, the proton nmr spectra (400MHz of 4 '-dimethoxy-N-(4-vinyl benzyl) pentanoic polymerizable organic phosphine oxygen compound neutral ligand; Solvent is a deuterochloroform, and confidential reference items are TMS): δ=7.378-7.457 (m, 12H); 7.298-7.368 (m, 10H), 7.194-7.248 (m; 4H), 6.739 (dd, J 1=9.2Hz, J 2=3.2Hz, 2H), 6.649 (q, J 1=10.8Hz, J 2=17.6Hz, 1H), 5.917 (dd, J 1=16.8Hz, J 2=2.8Hz, 2H), 5.660 (d, J=16.8Hz, 1H), 5.160 (d, J=10.8Hz, 1H), 4.678 (s, 2H), 3.400ppm (s, 6H); Flight time mass spectrum: m/z (%): 746 (100) M +Near infrared spectrogram (pressing potassium bromide troche, cm -1): 3051,2925,1628 (C=C stretching vibrations), 1482,1436 (C-P stretching vibrations), 1283,1235,1197 (P=O stretching vibrations), 1114,1044,993,749,718,701,531.Ultimate analysis (quality %) theoretical value: C75.69, H 5.54, and N 1.88, and O 8.58; Measured value: C 75.77, H 5.49, and N 2.09, and O 8.80.
Embodiment 14: what this embodiment and embodiment four were different is the polymerizable organic phosphine oxygen compound neutral ligand that adopts embodiment ten; Trifluoromethyl thiophene ethylacetoacetone anion ligand and trivalent europium ion rare earth central metallic ions complex reaction obtain, and the chemical formula brief note of polymerizable organic phosphine oxygen rare earth compounding is Eu (TTA) 3(VBCzDPO) 2, chemical structural formula is suc as formula shown in (IX):
Figure GSA00000027147400112
other parameter is identical with embodiment four.
The polymerizable organic phosphine oxygen rare earth compounding (Eu (TTA) of this embodiment 3(VBCzDPO) 2) proton nmr spectra (400MHz, solvent are deuterochloroform, and confidential reference items are TMS): δ=9.289-10.443 (m, 10H); 7.148-8.052 (m, 23H), 6.955 (s, 3H); 6.296-6.731 (m, 7H), 5.927-6.229 (br, 1H); 4.924-5.142 (br, 1H), 4.439-4.757ppm (br, 2H); Flight time mass spectrum: m/z (%): 1499 (100) [M +]; Near infrared spectrogram (pressing potassium bromide troche, cm -1): 3060,2975,1632 (C=C stretching vibrations), 1608 (C=O stretching vibrations), 1537 (the C=C stretching vibrations in the thienyl trifluoromethyl methyl ethyl diketone), 1504,1468; 1439 (C-P stretching vibrations), 1413,1357,1304,1245,1230,1180 (P=O stretching vibrations); 1142,1095,1061,934,784,726; 708,694,642,580,537,520; Ultimate analysis (quality %) theoretical value: C 55.28, H 3.16, and Eu 10.14, and N 0.93, and O 8.54, S6.42; Measured value: C 55.34, H 3.21, and Eu 9.99, and N 1.17, and O 8.68, and S 6.53.
Embodiment 15: what this embodiment and embodiment four were different is the polymerizable organic phosphine oxygen compound neutral ligand that adopts embodiment 11; Trifluoromethyl thiophene ethylacetoacetone anion ligand and trivalent europium ion rare earth central metallic ions complex reaction obtain, the Eu (TTA) of polymerizable organic phosphine oxygen rare earth compounding 3(VBmCzDPO) 2, chemical structural formula is suc as formula shown in (X):
Figure GSA00000027147400121
other parameter is identical with embodiment four.
Embodiment 16: what this embodiment and embodiment four were different is the polymerizable organic phosphine oxygen compound neutral ligand that adopts embodiment 12; Trifluoromethyl thiophene ethylacetoacetone anion ligand and trivalent europium ion rare earth central metallic ions complex reaction obtain, the Eu (TTA) of polymerizable organic phosphine oxygen rare earth compounding 3(TPADPO) 2, chemical structural formula is suc as formula shown in (XI):
Figure GSA00000027147400122
other parameter is identical with embodiment four.
Embodiment 17: what this embodiment and embodiment four were different is the polymerizable organic phosphine oxygen compound neutral ligand that adopts embodiment 13; Trifluoromethyl thiophene ethylacetoacetone anion ligand and trivalent europium ion rare earth central metallic ions complex reaction obtain, and polymerizable organic phosphine oxygen rare earth compounding is Eu (TTA) 3(TMOADPO) 2, its chemical structural formula is suc as formula shown in (XII):
Figure GSA00000027147400131
other parameter is identical with embodiment four.
The polymerizable organic phosphine oxygen rare earth compounding Eu (TTA) of this embodiment 3(TMOADPO) 2Proton nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS): δ=7.640-8.679 (br, 10H), 7.306-7.612 (br; 6H), and 6.477-7.292 (m, 27H), 5.584 (d, J=12.6Hz; 1H), 5.476 (s, 2H), 5.133 (d; J=10.8Hz, 1H), 3.616ppm (s, 6H).Flight time mass spectrum: m/z (%): 1561 (100) M +Near infrared spectrogram (pressing potassium bromide troche, cm -1): 3059,2950,1636 (C=O stretching vibrations), 1612 (C=O stretching vibrations), 1536 (C=C stretching vibration in TTA), 1483,1438 (C-P stretching vibrations); 1413,1354,1302,1229,1180 (P=O stretching vibrations), 1142,1060; 1041,933,855,780,749,723; 707,693,642,580,541,523.Ultimate analysis (quality %) theoretical value: C 54.62, H 3.42, and Eu 9.73, and N 0.90, and O 10.25, and S 6.16; Measured value: C54.69, H 3.45, and Eu 10.01, and N 1.19, and O 10.52, and S 6.33.
Embodiment 18: this embodiment unconjugated organic phosphorus, oxide rare earth coordination polymer is the polymerizable organic phosphine oxygen rare earth compounding Eu (TTA) with embodiment 14 3(VBCzDPO) 2With VCz as monomer, obtain through free-radical polymerized, unconjugated organic phosphorus, oxide rare earth coordination polymer chemical structural formula is shown in (XIII):
Figure GSA00000027147400132
be n: m=1 wherein: 99～10: 90; M+n=100; M, n are positive integer.
The unconjugated organic phosphorus, oxide rare earth coordination polymer brief note that this embodiment obtains is P1.
Embodiment 19: that this embodiment and embodiment 18 are different is n: m=1: 99.Other parameter is identical with embodiment 18.
The unconjugated organic phosphorus, oxide rare earth coordination polymer of this embodiment is designated as P1 1%
The P1 of this embodiment 1%Molecular weight: M n=9576, M w=17187, PDI=1.79, Eu 3+Content 0.79wt%.Wherein, M nBe number-average molecular weight, M wBe weight-average molecular weight, PDI is a molecular weight distributing index.
The P1 of this embodiment 1%Proton nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS): δ=7.701,7.195,7.016,6.917,6.557; 6.407,6.247,4.911,4.135,3.462,3.174,2.568; 1.792,1.561,1.442,1.277,1.079,0.898ppm.Carbon-13 nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS): δ=140.046,137.861,137.351,137.410; 125.351,125.050,123.821,122.189,121.979,120.249; 119.167,118.894,118.652,110.356,108.120,107.986; 107.780,107.496,50.175,49.314,48.195,36.126ppm.Near infrared spectrogram (pressing potassium bromide troche, cm -1): 3047,2929,1882,1624,1597,1538 (the C=C stretching vibrations in the thienyl trifluoromethyl methyl ethyl diketone), 1483,1452,1332,1223,1157,1124,1026,1003,923,840,744,720,420.Ultimate analysis (quality %) theoretical value: C 84.74, H 5.51, and N 6.79, and S 0.47, and O 0.62; Measured value: C 85.59, H 5.42, N6.93, S 0.59, and O 0.78.
This embodiment is to P1 1%Carry out the UVF spectrum test, test result is as shown in Figure 1.Curve 1 is the uv absorption spectrum curve among the figure, and curve 2 is the photoluminescence curve of spectrum; Can know P1 by curve among Fig. 11 1%Absorption peak and polyvinyl carbazole basic identical, show that vinyl carbazole in this polymkeric substance partly bears the absorption of energy; Can know P1 by curve 2 1%Two glow peaks are arranged, and at 375nm (emission peak of corresponding polyvinyl carbazole) and 612nm (emission peak of corresponding europium ion), the two strength ratio is 2: 1 respectively.
The test condition of this embodiment medium ultraviolet absorption spectrum is: room temperature, 10 -5Every liter of dichloromethane solution of mole.Photoluminescence spectrum test condition is a room temperature, excitation wavelength 280nm, 10 -5Every liter of dichloromethane solution of mole.
Embodiment 20: that this embodiment and embodiment 18 are different is n: m=3: 97.Other parameter is identical with embodiment 18.
The unconjugated organic phosphorus, oxide rare earth coordination polymer of this embodiment is designated as P1 3%
The P1 of this embodiment 3%Molecular weight: M n=6510, M w=9200, PDI=1.79.Eu 3+Content 2.05wt%.Draw n: m=3: 97.
The P1 of this embodiment 3%Proton nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS): δ=7.729,7.175,7.017,6.940,6.574; 6.445,6.243,5.001,4.148,3.505,3.250,2.566; 1.852,1.566,1.444,1.274,1.097,0.923ppm; Carbon-13 nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS): δ=140.096,137.917,137.353,137.411; 125.374,124.998,123.940,122.210,121.899,120.214; 119.203,118.891,118.634,110.352,108.124,107.989; 107.785,107.490,50.175,49.314,48.196,36.126ppm; Near infrared spectrogram (pressing potassium bromide troche, cm -1): 3048,2930,1882,1625,1598,1538 (the C=C stretching vibrations in the thienyl trifluoromethyl methyl ethyl diketone), 1483,1452,1333,1223,1157,1124,1026,1003,923,840,744,720,421; Ultimate analysis (%) theoretical value: C 80.90, H 5.20, and N 6.03, and S 1.24, and O 1.65; Measured value: C 81.79, H 5.05, and N 6.37, and S 1.36, and O 1.81.
Test condition in this embodiment employing embodiment 19 is to P1 3%Carry out the UVF spectrum test, test result is as shown in Figure 2.Curve 1 is the uv absorption spectrum curve among the figure, and curve 2 is the photoluminescence curve of spectrum; Can know P1 by curve among Fig. 21 3%Absorption peak and polyvinyl carbazole basic identical, show that vinyl carbazole in this polymkeric substance partly bears the absorption of energy; Can know P1 by curve 2 3%Two glow peaks are arranged, and at 375nm (emission peak of corresponding polyvinyl carbazole) and 612nm (emission peak of corresponding europium ion), the two strength ratio is 1: 6 respectively, explains that the content that increases europium ion can improve the efficient of intramolecular energy transfer.
Embodiment 21: the unconjugated organic phosphorus, oxide rare earth coordination polymer of this embodiment is the polymerizable organic phosphine oxygen rare earth compounding Eu (TTA) with embodiment 15 3(VBmCzDPO) 2With VCz as monomer, obtain through free-radical polymerized, unconjugated organic phosphorus, oxide rare earth coordination polymer chemical structural formula is shown in (XIV):
Figure GSA00000027147400151
be n: m=1 wherein: 99～10: 90; M+n=100; M, n are positive integer.
The unconjugated organic phosphorus, oxide rare earth coordination polymer brief note that this embodiment obtains is P2.
Embodiment 22: that this embodiment and embodiment 21 are different is n: m=1: 99.Other parameter is identical with embodiment 21.
Embodiment 23: that this embodiment and embodiment 21 are different is n: m=3: 97.Other parameter is identical with embodiment 21.
Embodiment 24: the unconjugated organic phosphorus, oxide rare earth coordination polymer of this embodiment is the polymerizable organic phosphine oxygen rare earth compounding Eu (TTA) with embodiment 16 3(TPADPO) 2With VCz as monomer, obtain through free-radical polymerized, unconjugated organic phosphorus, oxide rare earth coordination polymer chemical structural formula is shown in (XV):
be n: m=1 wherein: 99～10: 90; M+n=100; M, n are positive integer.
The unconjugated organic phosphorus, oxide rare earth coordination polymer brief note that this embodiment obtains is P3.
Embodiment 25: that this embodiment and embodiment 24 are different is n: m=1: 99.Other parameter is identical with embodiment 24.
Embodiment 26: that this embodiment and embodiment 24 are different is n: m=3: 97.Other parameter is identical with embodiment 24.
Embodiment 27: the unconjugated organic phosphorus, oxide rare earth coordination polymer of this embodiment is the polymerizable organic phosphine oxygen rare earth compounding Eu (TTA) with embodiment 17 3(TMOADPO) 2With VCz as monomer, obtain through free-radical polymerized, unconjugated organic phosphorus, oxide rare earth coordination polymer chemical structural formula is shown in (XVI):
Figure GSA00000027147400171
be n: m=1 wherein: 99～10: 90; M+n=100; M, n are positive integer.
The unconjugated organic phosphorus, oxide rare earth coordination polymer brief note that this embodiment obtains is P4.
Embodiment 28: that this embodiment and embodiment 27 are different is n: m=1: 99.Other parameter is identical with embodiment 27.
The unconjugated organic phosphorus, oxide rare earth coordination polymer of this embodiment is designated as P4 1%
The P4 of this embodiment 1%Molecular weight: M n=9518, M w=13408, PDI=1.41.Eu 3+Content is 0.84wt%, draws P4 1%N: m=1: 99.
The P4 of this embodiment 1%Proton nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS): δ=7.731,7.175,7.018,6.919,6.557; 6.425,6.233,4.920,4.135,3.531,3.279,2.566; 1.821,1.569,1.443,1.274,1.089,0.909ppm.Carbon-13 nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS): δ=140.053,137.844,137.351,137.412; 125.371,125.048,123.899,122.272,122.004,120.255; 119.217,118.854,118.509,110.356,108.120,107.891; 107.763,107.410,50.176,49.310,48.195,36.128ppm.Near infrared spectrogram (pressing potassium bromide troche, cm -1): 3048,2931,1625,1598,1535 (the C=C stretching vibrations in the thienyl trifluoromethyl methyl ethyl diketone), 1483,1453,1332,1223,1157,1124,1026,1000,923,840,744,720.Ultimate analysis (quality %) theoretical value: C 84.57, H 5.56, and N 6.77, and S 0.46, and O 0.77; Measured value: C 84.93, H 5.64, and N 7.00, and S 0.62, and O 0.89.
Test condition in this embodiment employing embodiment 19 is to P4 1%Carry out the UVF spectrum test, test result is as shown in Figure 3.Curve 1 is the uv absorption spectrum curve among Fig. 3, and curve 2 is the photoluminescence curve of spectrum; Can know P4 by curve among Fig. 31 1%Absorption peak and polyvinyl carbazole basic identical, show that vinyl carbazole in this polymkeric substance partly bears the absorption of energy; Can know P4 by curve 2 1%Two glow peaks are arranged, and at 375nm (emission peak of corresponding polyvinyl carbazole) and 612nm (emission peak of corresponding europium ion), the two strength ratio is 1: 1 respectively.
Embodiment 29: that this embodiment and embodiment 27 are different is n: m=3: 97.Other parameter is identical with embodiment 27
The unconjugated organic phosphorus, oxide rare earth coordination polymer of this embodiment is designated as P4 3%
The P4 of this embodiment 3%Molecular weight: M n=6501, M w=8790, PDI=1.35, Eu 3+Content is 2.17wt%.Draw P4 3%N: m=3: 97.Wherein, M nBe number-average molecular weight, M wBe weight-average molecular weight, PDI is a molecular weight distributing index.
The P4 of this embodiment 3%Proton nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS): δ=7.733,7.181,7.000,6.934,6.581; 6.449,6.247,4.998,4.129,3.517,3.251,2.566; 1.853,1.571,1.445,1.274,1.090,0.924ppm.Carbon-13 nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS): δ=140.113,137.927,137.353,137.415; 125.378,124.908,123.918,122.210,121.874,120.216; 119.211,118.924,118.636,110.358,108.147,107.868; 107.786,107.459,50.188,49.364,48.212,36.154ppm.Near infrared spectrogram (pressing potassium bromide troche, cm -1): 3046,2925,1624,1597,1535 (the C=C stretching vibrations in the thienyl trifluoromethyl methyl ethyl diketone), 1483,1452,1324,1222,1156,1123,1023,1000,922,744,720,420; Ultimate analysis (%) theoretical value: C80.54, H 5.27, and N 5.98, and S 1.23, and O 2.05; Measured value: C 80.82, H 5.31, and N 6.20, and S 1.39, and O 2.27.
Test condition in this embodiment employing embodiment 19 is to P4 3%Carry out the UVF spectrum test, test result is as shown in Figure 4.Curve 1 is the uv absorption spectrum curve among Fig. 4, and curve 2 is the photoluminescence curve of spectrum; Can know P4 by curve among Fig. 41 3%Absorption peak and polyvinyl carbazole basic identical, show that vinyl carbazole in this polymkeric substance partly bears the absorption of energy; Can know P4 by curve 2 3%Two glow peaks are arranged, and at 375nm (emission peak of corresponding polyvinyl carbazole) and 612nm (emission peak of corresponding europium ion), the two strength ratio is 1: 6 respectively, explains that the content that increases europium ion can improve the efficient of intramolecular energy transfer.
Embodiment 30: this embodiment is that the preparation method of practical implementation one described non-conjugated organic phosphine oxygen rare earth coordination polymer is: with polymerizable organic phosphine oxygen compound rare earth compounding and VCz is that 1: 1.3～100 ratio adds in the organic solvent in molar ratio; And then adding radical initiator; At inert gas atmosphere, 60～80 ℃ of following reaction 10～90h, behind sedimentation, separation, extraction, drying, desolventizing, promptly get the unconjugated organic phosphorus, oxide rare earth coordination polymer more then; Wherein organic solvent is THF or methylene dichloride; The ratio of VCz molar weight and organic solvent volume is 1mmol: 0.5～10mL; Radical initiator is azo-initiator or peroxide initiator, and the molar weight of radical initiator is 5% of polymerizable organic phosphine oxygen compound rare earth compounding and a VCz integral molar quantity.
Rare gas element is argon gas or helium in this embodiment.The preparation method of unconjugated organic phosphorus, oxide rare earth coordination polymer of the present invention is simple, and the cycle is short, and cost is low.
The embodiment hentriaconta-: what this embodiment and embodiment 30 were different is that radical initiator is Diisopropyl azodicarboxylate (AIBN), Lucidol etc.Other step and parameter are identical with embodiment 30.
In this embodiment radical initiator do not limit with more than cited kind, everyly be easy to generate stable radical, cause chain initiation, cause that radical chain type polymeric azo-initiator or peroxide initiator all can be used for this embodiment.
Embodiment 32: what this embodiment was different with embodiment 30 or hentriaconta-is at argon gas atmosphere, 60 ℃ of following reaction 72h.Other step and parameter are identical with embodiment 30 or hentriaconta-.
Embodiment 33: this embodiment and embodiment 30, hentriaconta-or 32 different be that the preparation method of polymerizable organic phosphine oxygen compound rare earth compounding is: three normal beta-diketons are dissolved in the organic solvent; Add the aqueous sodium hydroxide solution that contains three Equivalent Hydrogen sodium oxides again; Then behind reaction 15～30min under 60 ℃; Add again behind the rare earth soluble salt of monovalent at 60 ℃ of reaction 30～60min down; And then in the polymerizable organic phosphine oxygen compound adding previous reaction system with monovalent; Reacted 2～8 hours down at 60～70 ℃ then, behind extraction, separation, drying, desolventizing, recrystallization gets polymerizable organic phosphine oxygen rare earth compounding more then; Wherein, the ratio of the molar weight of beta-diketon and organic solvent volume is 3mmol: 10mL, and organic solvent is alcohols, THF or methylene dichloride.
The volumetric molar concentration of aqueous sodium hydroxide solution is 1～3mol/L in this embodiment.
Embodiment 34: what this embodiment and embodiment 33 were different is that the rare earth soluble salt is EuCl 36H 2O, Eu (NO 3) 36H 2O, Eu (ac) 36H 2O.Other step and parameter are identical with embodiment 33.
Embodiment 35: this embodiment is different with practical implementation 33 or 34 is that the preparation method of polymerizable organic phosphine oxygen compound realizes through following steps: one, be dissolved under the alkaline system that reaction solvent constitutes at room temperature, inorganic base aqueous solution or organic bases; With purifying to such an extent that vinyl benzyl replaces the Ar bromide behind Ar bromide and the vinyl chloride hybrid reaction 12～18h, wherein the mol ratio of Ar bromide and vinyl chloride is 1: 1～2; Two, the vinyl benzyl that step 1 is obtained replaces the Ar bromide and adds in the organic solvent after anhydrous and oxygen-free is handled, and stirring and dissolving gets mixed system, then mixed system is cooled to-78～0 ℃; Insulation drips n-Butyl Lithium afterreaction 1～2h again in mixed system, react 0.5～1h again after being warming up to room temperature then; And then mixed system is cooled to-78～0 ℃, insulation is after diethyl ether solution or the volumetric concentration that drips volumetric concentration again and be 50% diphenyl phosphine chloride is the tetrahydrofuran solution of 50% diphenyl phosphine chloride; Reaction 1～3h; Be warming up to room temperature afterreaction 8～24h again, purify and obtain the organic phosphine oxygen compound, wherein; Organic solvent is anhydrous diethyl ether or THF; The mol ratio that vinyl benzyl replaces Ar bromide and n-Butyl Lithium is 1: 2～2.5, and the ratio that vinyl benzyl replaces Ar bromide and organic solvent is 1mmol: 5mL, and the mol ratio that vinyl benzyl replaces Ar bromide and diphenyl phosphine chloride is 1: 1; Three, the organic phosphine oxygen compound that step 2 is obtained adds in the organic solvent, and stirring and dissolving adds ydrogen peroxide 50 again; And then react 2～4h under the room temperature, obtain polymerizable organic phosphine oxygen compound, wherein; Organic solvent is 1; 4-dioxane, methylene dichloride, chloroform etc., the ratio of organic phosphine oxygen compound and organic solvent is 1mmol: 5mL, H in organic phosphine oxygen compound and the ydrogen peroxide 50 2O 2Mol ratio be 1: 1～1.5.Other step and parameter are identical with embodiment 33 or 34.
N-Butyl Lithium is the commercially available prod in this embodiment; The commercially available prod is generally n-Butyl Lithium is dissolved in the organic solvents such as hexane, hexanaphthene, Skellysolve A, and needing only the molar weight of assurance n-Butyl Lithium and the mol ratio of vinyl benzyl replacement Ar bromide in this embodiment is 2～2.5: 1.
Embodiment 36: what this embodiment and embodiment 35 were different is that the Ar bromide is 3 in the step 1,6-dibromo carbazole, 2,2 '-two bromo-4,4 '-dimethoxy pentanoic, 4,5-dibromo carbazole, 2,2 '-dibromo pentanoic etc.
Embodiment 37: what this embodiment was different with embodiment 35 or 36 is step 1: with 3 of 10mmol; 6-dibromo carbazole (3.25g) and 1mmol Tetrabutyl amonium bromide (210mg) are dissolved in the 50mL DMSO 99.8MIN. (DMSO); Add the 6mLKOH aqueous solution (2mol/L) again, at room temperature stir then the 4-vinyl chloride that adds 12mmol after half hour again (1.3mL, 1.84g); Right lucifuge stirring reaction 16h at room temperature; To pour into then in the water, with dichloromethane extraction, organic layer is with anhydrous MgSO 4Drying is revolved driedly, crosses post and gets 3,6-two bromo-N-(4-vinyl benzyl) carbazole.Other step and parameter and embodiment 35 or 30 six phases are together.
The product 3 of this embodiment, 6-two bromo-N-(4-vinyl benzyl) carbazole is a white powder, obtains 3.98g behind the post excessively, productive rate is 90%.
The proton nmr spectra of the product that this embodiment obtains (400MHz, solvent are deuterochloroform, and confidential reference items are TMS): δ=8.180 (s, 2H), 7.534 (d; J=8.4Hz, 2H), 7.311 (d, J=8.4Hz, 2H); 7.238 (d, J=8.8Hz, 2H), 7.029 (d; J=8.0Hz, 2H), 6.682 (q, J 1=10.8Hz, J 2=17.6Hz, 1H), 5.710 (d, J=17.6Hz, 1H), 5.454 (s, 2H), 5.234ppm (d, J=10.8Hz, 1H); Gaseous mass spectrum: m/z (%): 441 (100) [M +]; Ultimate analysis (quality %) theoretical value: C 57.17, H 3.43, and N 3.17; Measured value: C 57.22, H 3.41, and N 3.43.Can know that the product of this embodiment is 3,6-two bromo-N-(4-vinyl benzyl) carbazole.
Embodiment 38: the preparation method of this embodiment polymerizable organic phosphine oxygen compound realizes through following steps: one, with the embodiment 37 of 10mmol obtain 3; Stirring and dissolving gets mixed system in the 50mL ether of 6-two bromo-N-(4-vinyl benzyl) carbazole adding after anhydrous and oxygen-free is handled, and then mixed system is cooled to-78 ℃, insulation; In mixed system, drip n-Butyl Lithium (n-BuLi) the hexane solution afterreaction 1h of the 1.6mol/L of 15mL again; React 1h again after being warming up to room temperature then, and then mixed system is cooled to-78 ℃, insulation; After dripping volumetric concentration again and be the diethyl ether solution of 50% diphenyl phosphine chloride; Reaction 1h is warming up to room temperature afterreaction 15h again, obtains organic phosphine compound through column chromatography purification then; Two, the step 1 with 1mmol obtains organic phosphine oxygen compound (638mg) adding 5mL 1, in the 4-dioxane, and stirring and dissolving; The ydrogen peroxide 50 that adds 0.11mL 30% (quality) again; At room temperature react 4h then, refilter, drying obtains polymerizable organic phosphine oxygen compound.
This embodiment step 1 obtains the 4.45g organic phosphine compound, and productive rate reaches 65%, is pale yellow powder.
The polymerizable organic phosphine oxygen compound that this embodiment obtains is 3, and 6-diphenylphosphine oxo-N-(4-vinyl benzyl) carbazole is white powder.The productive rate of step 2 reaches 99%.
This enforcement is carried out proton nmr spectra (400MHz, solvent are deuterochloroform, and confidential reference items are TMS), flight time mass spectrum, near infrared spectrogram (pressing potassium bromide troche, cm to the polymerizable organic phosphine oxygen compound that obtains -1) and the ultimate analysis test, test result is identical with the test result of embodiment ten.Prove that the polymerizable organic phosphine oxygen compound that this embodiment obtains is 3,6-diphenylphosphine oxo-N-(4-vinyl benzyl) carbazole, structural formula is the same with the structure formula V of embodiment ten.
Embodiment 39: the preparation method of this embodiment polymerizable organic phosphine oxygen compound rare earth compounding is: with the thienyl trifluoromethyl methyl ethyl diketone (TTA of 3mmol; 672.7mg) be dissolved in the 10mL ethanol; The sodium hydroxide that adds 3mmol again; Behind reaction 30min under 60 ℃, add the EuCl of 1mmol more then 36H 2O (370.1mg) back is reacted 30min down at 60 ℃; And then with the embodiment 38 of 1mmol obtain 3; 6-diphenylphosphine oxo-N-(4-vinyl benzyl) carbazole adds in the previous reaction system; Reacted 8 hours down at 60 ℃ then, behind extraction, separation, drying, desolventizing, recrystallization gets polymerizable organic phosphine oxygen rare earth compounding Eu (TTA) more then 3(VBCzDPO) 2
The form of all right 2mol/L aqueous sodium hydroxide solution of sodium hydroxide adds in this embodiment, and add-on is 1.5mL.
The Eu that this embodiment obtains (TTA) 3(VBCzDPO) 2Be white powder, productive rate reaches 71%.
This embodiment carries out proton nmr spectra (400MHz, solvent are deuterochloroform, and confidential reference items are TMS), flight time mass spectrum, near infrared spectrogram (pressing potassium bromide troche, cm respectively to the polymerizable organic phosphine oxygen rare earth compounding that obtains -1) and the ultimate analysis test, the result is consistent with the test result of embodiment 14 for the test gained.Prove that the product that this embodiment obtains is polymerizable organic phosphine oxygen rare earth compounding Eu (TTA) 3(VBCzDPO) 2, record is consistent in structural formula and the embodiment 14.
Embodiment 40: the preparation method of the non-conjugated organic phosphine oxygen of this embodiment rare earth coordination polymer is: the polymerizable organic phosphine oxygen compound rare earth compounding Eu (TTA) that 0.060mmol embodiment 39 is obtained 3(VBCzDPO) 2(89.36mg) VCz (1.16g) with 6mmol adds in the 5mL anhydrous tetrahydro furan; And then add the 0.003mmol Diisopropyl azodicarboxylate (AIBN, 10mg), then argon gas atmosphere, 60 ℃ down behind the reaction 72h; In reaction system, adding the 5mL THF dilutes; Then with the methyl alcohol sedimentation, sedimentation and filtration was with apparatus,Soxhlet's (acetone) purifying 2 days, and vacuum drying oven is drying to obtain non-conjugated organic phosphine oxygen rare earth coordination polymer.
The product of this embodiment is thread white solid, and yield is 78%.
This embodiment has carried out proton nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS), carbon-13 nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS), near infrared spectrogram (pressing potassium bromide troche, cm respectively to product -1) and the ultimate analysis test, test result is the same with the test result of embodiment 19.
The product of this embodiment is the P1 of embodiment 19 1%, molecular weight: M n=9576, M w=17187, PDI=1.79, Eu 3+Content 0.79wt%.Draw n: m=1: 99.
Simultaneously, this embodiment is to P1 1%Carry out the uv absorption spectrum test, the spectrogram that test obtains is consistent with spectrogram (Fig. 1) result of embodiment 19.
Embodiment 41: the preparation method of the non-conjugated organic phosphine oxygen of this embodiment rare earth coordination polymer is: the polymerizable organic phosphine oxygen compound rare earth compounding Eu (TTA) that 0.21mmol embodiment 39 is obtained 3(VBCzDPO) 2(300.99mg) VCz (1.16g) with 6mmol adds in the 5mL anhydrous tetrahydro furan; And then add the 0.003mmol Lucidol (PBO, 7.2mg), then argon gas atmosphere, 60 ℃ down behind the reaction 72h; In reaction system, adding the 5mL THF dilutes; Then with the methyl alcohol sedimentation, sedimentation and filtration was with apparatus,Soxhlet's (acetone) purifying 2 days, and vacuum drying oven is drying to obtain non-conjugated organic phosphine oxygen rare earth coordination polymer.
The product of this embodiment is thread white solid, and yield is 55%.
This embodiment has carried out proton nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS), carbon-13 nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS), near infrared spectrogram (pressing potassium bromide troche, cm respectively to product -1) and the ultimate analysis test, test result is the same with the test result of embodiment 20.Obtain the non-conjugated organic phosphine oxygen rare earth coordination polymer P1 consistent with the structural formula of embodiment 20 3%
The product of this embodiment is the P1 of embodiment 20 3%, molecular weight is: M n=6510, M w=9200, PDI=1.79.Eu 3+Content 2.05wt%.Draw n: m=3: 97.
Simultaneously, this embodiment is to P1 3%Carry out the uv absorption spectrum test, the spectrogram that test obtains is consistent with spectrogram (Fig. 2) result of embodiment 20.
Embodiment 42: what this embodiment was different with embodiment 35 or 36 is step 1: with 2 of 10mmol; 2 '-two bromo-4,4 '-dimethoxy pentanoic (3.87g) and 1mmol Tetrabutyl amonium bromide (210mg) are dissolved in the 50mL DMSO 99.8MIN. (DMSO), add the 6mLKOH aqueous solution (2mol/L) again; At room temperature stir the 4-vinyl chloride (1.3mL that adds 12mmol after half hour more then; 1.84g), so lucifuge stirring reaction 16h at room temperature will pour in the water then; With dichloromethane extraction, organic layer is with anhydrous MgSO 4Drying is revolved driedly, crosses post and gets 2,2 '-two bromo-4,4 '-dimethoxy-N-(4-vinyl benzyl) pentanoic.Other step and parameter and embodiment 35 or 30 six phases are together.
Product 2,2 '-two bromo-4 of this embodiment, 4 '-dimethoxy-N-(4-vinyl benzyl) pentanoic is a white powder, obtains 4.78g behind the post excessively, productive rate is 95%.
2,2 '-two bromo-4 of this embodiment, the proton nmr spectra of 4 '-dimethoxy-N-(4-vinyl benzyl) pentanoic (400MHz, solvent are deuterochloroform, and confidential reference items are TMS): δ=7.454 (d; J=8.0Hz, 2H), 7.289 (d, J=8.0Hz, 2H); 7.123 (d, J=2.4Hz, 2H), 6.853 (d; J=8.8Hz, 2H), 6.690 (q, J 1=8.8Hz, J 2=2.4Hz, 2H), 6.637 (dd, J 1=6.4Hz, J 2=11.2Hz, 1H), 5.654 (d, J=17.6Hz, 1H), 5.157 (d, J=10.8Hz, 1H), 4.689 (s, 2H), 3.737ppm (s, 6H).Gaseous mass spectrum: m/z (%): 503 (100) M +Ultimate analysis (quality %) theoretical value: C 54.90, H 4.21, and N 2.78; Measured value: C 55.12, H 4.29, and N 3.11.
Embodiment 43: the preparation method of this embodiment polymerizable organic phosphine oxygen compound realizes through following steps: 2,2 '-two bromo-4 that, the embodiment 42 of 10mmol obtained, 4 '-dimethoxy-N-(4-vinyl benzyl) pentanoic add that stirring and dissolving gets mixed system in the 50mL ether after anhydrous and oxygen-free is handled; Then mixed system is cooled to-78 ℃; Insulation drips n-Butyl Lithium (n-BuLi) the hexane solution afterreaction 1h of the 1.6mol/L of 15mL again in mixed system, react 1h again after being warming up to room temperature then; And then mixed system is cooled to-78 ℃; Insulation, drip volumetric concentration again and be the tetrahydrofuran solution of 50% diphenyl phosphine chloride after, reaction 1h; Be warming up to room temperature afterreaction 8～24h again, obtain organic phosphine compound through column chromatography purification then; Two, the step 1 with 1mmol obtains organic phosphine oxygen compound (638mg) adding 5mL 1, in the 4-dioxane, and stirring and dissolving; The ydrogen peroxide 50 that adds 0.11mL 30% (quality) again; At room temperature react 4h then, filter then, drying obtains polymerizable organic phosphine oxygen compound.
The molar weight of the n-Butyl Lithium that adds in this embodiment is 24mmol.
This embodiment step 1 obtains the 4.45g organic phosphine compound, and productive rate reaches 65%, is pale yellow powder.
The polymerizable organic phosphine oxygen compound that this embodiment obtains is 2,2 '-diphenylphosphine oxo-4, and 4 '-dimethoxy-N-(4-vinyl benzyl) pentanoic is white powder.The productive rate of step 2 reaches 100%.
This enforcement is carried out proton nmr spectra (400MHz, solvent are deuterochloroform, and confidential reference items are TMS), flight time mass spectrum, near infrared spectrogram (pressing potassium bromide troche, cm respectively to the polymerizable organic phosphine oxygen compound that obtains -1) and the ultimate analysis test, test result is identical with the test result of embodiment ten.Prove that the polymerizable organic phosphine oxygen compound that this embodiment obtains is 2,2 '-diphenylphosphine oxo-4,4 '-dimethoxy-N-(4-vinyl benzyl) pentanoic, structural formula is the same with the structural formula (VIII) of embodiment 13.
Embodiment 44: the preparation method of this embodiment polymerizable organic phosphine oxygen compound rare earth compounding is: with the thienyl trifluoromethyl methyl ethyl diketone (TTA of 3mmol; 672.7mg) be dissolved in the 10mL ethanol; The sodium hydroxide that adds 3mmol again; Behind reaction 30min under 60 ℃, add the EuCl of 1mmol more then 36H 2O (370.1mg) back is reacted 30min down at 60 ℃; And then with the embodiment 43 of 1mmol obtain 2; 2 '-diphenylphosphine oxo-4,4 '-dimethoxy-N-(4-vinyl benzyl) pentanoic add in the previous reaction system, react 8 hours down at 60 ℃ then; Behind extraction, separation, drying, desolventizing, recrystallization gets polymerizable organic phosphine oxygen rare earth compounding Eu (TTA) more then 3(TMOADPO) 2
The form of all right 2mol/L aqueous sodium hydroxide solution of sodium hydroxide adds in this embodiment, and add-on is 1.5mL.
The Eu that this embodiment obtains (TTA) 3(TMOADPO) 2Be white powder, productive rate reaches 77%.
This embodiment carries out proton nmr spectra (400MHz, solvent are deuterochloroform, and confidential reference items are TMS), flight time mass spectrum, near infrared spectrogram (pressing potassium bromide troche, cm respectively to the polymerizable organic phosphine oxygen rare earth compounding that obtains -1) and the ultimate analysis test, the result is consistent with the test result of embodiment 17 for the test gained.Prove that the product that this embodiment obtains is polymerizable organic phosphine oxygen rare earth compounding Eu (TTA) 3(TMOADPO) 2, record is consistent in structural formula and the embodiment 17.
Embodiment 45: the preparation method of the non-conjugated organic phosphine oxygen of this embodiment rare earth coordination polymer is: the polymerizable organic phosphine oxygen compound rare earth compounding Eu (TTA) that 0.060mmol embodiment 44 is obtained 3(TMOADPO) 2(93.66mg) VCz (1.16g) with 6mmol adds in the 5mL anhydrous tetrahydro furan; And then adding 0.003mmol ABVN (12mg);, in reaction system, add the 5mL THF and dilute, down behind the reaction 72h argon gas atmosphere, 60 ℃ then then with the methyl alcohol sedimentation; Sedimentation and filtration was with apparatus,Soxhlet's (acetone) purifying 2 days, and vacuum drying oven is drying to obtain non-conjugated organic phosphine oxygen rare earth coordination polymer.
The product of this embodiment is thread white solid, and yield is 78%.
This embodiment has carried out proton nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS), carbon-13 nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS), near infrared spectrogram (pressing potassium bromide troche, cm respectively to product -1) and the ultimate analysis test, test result is the same with the test result of embodiment 28.
The product of this embodiment is the P4 of embodiment 28 1%, molecular weight: M n=9518, M w=13408, PDI=1.41.Eu 3+Content is 0.84wt%, i.e. P4 1%N: m=1: 99.
Simultaneously, this embodiment is to P4 1%Carry out the uv absorption spectrum test, the spectrogram that test obtains is consistent with spectrogram (Fig. 3) result of embodiment 28.
Embodiment 46: the preparation method of the non-conjugated organic phosphine oxygen of this embodiment rare earth coordination polymer is: the polymerizable organic phosphine oxygen compound rare earth compounding Eu (TTA) that 0.2mmol embodiment 44 is obtained 3(TMOADPO) 2(312.2mg) VCz (1.16g) with 6mmol adds in the 5mL anhydrous tetrahydro furan; And then add the 0.003mmol Diisopropyl azodicarboxylate (AIBN, 10mg), then argon gas atmosphere, 60 ℃ down behind the reaction 72h; In reaction system, adding the 5mL THF dilutes; Then with the methyl alcohol sedimentation, sedimentation and filtration was with apparatus,Soxhlet's (acetone) purifying 2 days, and vacuum drying oven is drying to obtain non-conjugated organic phosphine oxygen rare earth coordination polymer.
The product of this embodiment is thread white solid, and yield is 78%.
This embodiment has carried out proton nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS), carbon-13 nmr spectra (300MHz, solvent are deuterochloroform, and confidential reference items are TMS), near infrared spectrogram (pressing potassium bromide troche, cm respectively to product -1) and the ultimate analysis test, test result is the same with the test result of embodiment 29.
The product of this embodiment is the P4 of embodiment 29 3%, molecular weight: M n=6501, M w=8790, PDI=1.35, Eu 3+Content is 2.17wt%.Draw P4 3%N: m=3: 97.
Simultaneously, this embodiment is to P4 3%Carry out the uv absorption spectrum test, the spectrogram that test obtains is consistent with spectrogram (Fig. 4) result of embodiment 28.
Embodiment 47: this embodiment is the application of embodiment one described non-conjugated organic phosphine oxygen rare earth coordination polymer as luminescent layer material in the electroluminescent device or luminescent layer dopant material.
The bright voltage that opens of the electroluminescent device that this embodiment obtains is 12.5～21V, and current density can reach 60～265mA/cm 2, electroluminescent brightness can reach 15～150cd/m 2
Embodiment 48: this embodiment and embodiment 47 are different be when non-conjugated organic phosphine oxygen rare earth coordination polymer as electroluminescent device in during the luminescent layer dopant material; Luminescent layer is embodiment one described non-conjugated organic phosphine oxygen rare earth coordination polymer and 2-phenyl-5-(4-tert-butyl-phenyl)-1; 3, the adulterate body that 4-oxadiazole (PBD) is formed.Other parameter is identical with embodiment 47.
PBD accounts for 30% (quality) of adulterate body in this embodiment.
Embodiment 49: this embodiment is different with embodiment 47 or 48 is that the luminescent layer of electroluminescent device is between hole injection layer and electric transmission/hole blocking layer.Other parameter is identical with embodiment 47 or 48.
The thickness of luminescent layer is 10～100nm in this embodiment, and the thickness of hole injection layer is 20～60nm, and the thickness of electric transmission/hole blocking layer is 10～80nm.
This embodiment holes input horizon can improve the anodic hole to be injected and transmits, and the electronics that electric transmission/hole blocking layer can improve negative electrode injects and transmission, makes charge energy compound well at luminescent layer, improves luminous efficiency.
Can also be between luminescent layer and hole injection layer in this embodiment spin coating hole transport/electronic barrier layer, further improve the anodic hole and inject and laser propagation effect.
Embodiment 50: this embodiment and embodiment 47,48 or 49 are different is to utilize vacuum thermal evaporation technology coating/vapor deposition electron transfer layer, electron injecting layer and negative electrode successively on electric transmission/hole blocking layer.Other parameter is identical with embodiment 47,48 or 49.
If adopt electric transmission/hole blocking layer that enough electronic transmission performances can be provided, can electron transfer layer be saved in this embodiment, directly vapor deposition electron injecting layer and negative electrode.
Embodiment 51: this embodiment and embodiment 47 to 50 are different is that the negative electrode of electroluminescent device is made up of calcium, magnesium, aluminium, silver or its alloy material; Anode is made up of tin indium oxide (ITO) or transparent conductive polymer.Other parameter is identical with practical implementation 47 to 50.
The thickness of negative electrode is 100～1000nm in this embodiment.Anode is the commercially available prod.
Cathode material is the metal or the semi-transparent conductor that can produce reflection in this embodiment, is not limited to the material that this embodiment is enumerated; When cathode material is aluminium, must be at aluminium cathode surface vapor deposition one deck LiF.
Embodiment 52: this embodiment and embodiment 51 are different is anode when being made up of transparent conductive polymer, and transparent conductive polymer is a polyaniline.Other parameter is identical with practical implementation 51.
Embodiment 53: this embodiment and embodiment 47 to 52 are different is that the structure of electroluminescent device is followed successively by anode, hole injection layer, luminescent layer, electric transmission/hole blocking layer, electron transfer layer, electron injecting layer and negative electrode.Other parameter is identical with embodiment 47 to 52.
Anode is plated on the residuites such as glass or plastics in this embodiment through the vapor deposition mode; Hole injection layer is through spin coating or inkjet technology film forming on anode; Luminescent layer deposits on the hole injection layer through spin coating or ink-jet printing process; Electric transmission/hole blocking layer deposits on the luminescent layer through thermal evaporation techniques; Negative electrode deposits on electric transmission/hole blocking layer through thermal evaporation techniques.
Embodiment 54: the non-conjugated organic phosphine oxygen of this embodiment rare earth coordination polymer is as the application of the luminescent layer material in the electroluminescent device, and the luminescent layer material is the P1 that embodiment 39 obtains in the electroluminescent device 1%, thickness is 80nm; Anode material is that resistance is 10 -20The indium oxide tin glass of Ω/square centimeter, the hole injection layer material is for gathering 3,4-ethylenedioxy thiophene: polyvinyl sulfonate (PEDOT: PSS, volume ratio 1: 1), thickness is 40nm; The material of electron injecting layer is Ba, and thickness is 4nm; Cathode material is an aluminium, and thickness is 120nm.
The structure of electroluminescent device is in this embodiment: and ITO/PEDOT:PSS (40nm)/Copolymer:PBD (80nm) (30%, 80nm)/Ba (4nm)/Al (120nm).Electroluminescent device prepares the method described in the embodiment 53 that adopts in this embodiment.
Embodiment 55: what this embodiment and embodiment 54 were different is the application of non-conjugated organic phosphine oxygen rare earth coordination polymer as the luminescent layer dopant material in the electroluminescent device, and the luminescent layer dopant material is the P1 that embodiment 40 obtains 1%With 2-phenyl-5-(4-tert-butyl-phenyl)-1,3, the adulterate body that 4-oxadiazole (PBD) is formed, PBD is 30% (quality) of adulterate body.Other parameter is identical with embodiment 54.
This embodiment carries out characteristic of semiconductor and electroluminescent properties test to the electroluminescent device that obtains; Current-voltage-brightness curve figure that test obtains; As shown in Figure 5; "--zero--" is the voltage-to-current densimetric curve among the figure, and
Figure GSA00000027147400281
is voltage-brightness curve.Can be known that by Fig. 5 the bright voltage that opens of electroluminescent device is 13V in this embodiment, maximum current density is 265mA/cm 2, maximum electrical photoluminescence brightness is 36cd/m 2The P1 of this embodiment 1%The maximum external quantum efficiency that is applied to electroluminescent device can reach 0.037%.
This embodiment carries out the electroluminescent spectrum test to the electroluminescent device that obtains, and TV is 0-20V, voltage spaces 1V, and the TV numerical value in the difference corresponding diagram 5, test result electroluminescent spectrum figure is shown in Fig. 6 (13V, 14V, 15V and 16V).From Fig. 6, can know P1 1%The characteristic emission peak that only comprises europium ion, main peak are at 615nm, for pure red luminous.
Embodiment 56: this embodiment and embodiment 54 are different is that non-conjugated organic phosphine oxygen rare earth coordination polymer in the luminous layer dopant material is the P1 that embodiment 41 obtains 3%Other parameter is identical with embodiment 54.
This embodiment carries out characteristic of semiconductor and electroluminescent properties test to the electroluminescent device that obtains; Current-voltage-brightness curve figure that test obtains; As shown in Figure 7; "--zero--" is the voltage-to-current densimetric curve among the figure, and
Figure GSA00000027147400291
is voltage-brightness curve.Can be known that by Fig. 7 the bright voltage that opens of electroluminescent device is 16V in this embodiment, maximum current density is 106.8mA/cm 2, maximum electrical photoluminescence brightness is 15cd/m 2The P1 of this embodiment 3%The maximum external quantum efficiency that is applied to electroluminescent device can reach 0.012%.
Embodiment 57: this embodiment and embodiment 54 are different is that non-conjugated organic phosphine oxygen rare earth coordination polymer in the luminous layer dopant material is the P4 that embodiment 45 obtains 1%Other parameter is identical with embodiment 54.
This embodiment carries out characteristic of semiconductor and electroluminescent properties test to the electroluminescent device that obtains; Current-voltage-brightness curve figure that test obtains; As shown in Figure 8; "--zero--" is the voltage-to-current densimetric curve among the figure, and
Figure GSA00000027147400292
is voltage-brightness curve.Can be known that by Fig. 8 the bright voltage that opens of electroluminescent device is 12.5V in this embodiment, maximum current density is 96mA/cm 2, maximum electrical photoluminescence brightness is 149cd/m 2The P4 of this embodiment 1%The maximum external quantum efficiency that is applied to electroluminescent device can reach 0.43%.
This embodiment carries out the electroluminescent test to the electroluminescent device that obtains, and TV is 0-20V, voltage spaces 0.5V, and the TV numerical value in the difference corresponding diagram 8, the test result electroluminescent spectrum is shown in Fig. 9 (12.5V, 13V and 14V).From Fig. 9, can know, from figure, can know P4 1%The characteristic emission peak that only comprises europium ion, main peak are at 615nm, for pure red luminous.
Embodiment 58: this embodiment and embodiment 54 are different is that non-conjugated organic phosphine oxygen rare earth coordination polymer in the luminous layer dopant material is the P4 that embodiment 46 obtains 3%Other parameter is identical with embodiment 54.
This embodiment carries out characteristic of semiconductor and electroluminescent properties test to the electroluminescent device that obtains; Current-voltage-brightness curve figure that test obtains; Shown in figure 10; "--zero--" is the voltage-to-current densimetric curve among the figure, and
Figure GSA00000027147400301
is voltage-brightness curve.Can be known that by Figure 10 the bright voltage that opens of electroluminescent device is 21V in this embodiment, maximum current density is 60mA/cm 2, maximum electrical photoluminescence brightness is 43cd/m 2The P4 of this embodiment 3%The maximum external quantum efficiency that is applied to electroluminescent device can reach 0.185%.
Embodiment 59: this embodiment is the application of embodiment one described non-conjugated organic phosphine oxygen rare earth coordination polymer as the electroactive layer of electrostrictive polymer memory device.
Embodiment 60: this embodiment and embodiment 59 are different is that the thickness of the electroactive layer of electrostrictive polymer memory device is 40～60nm.Other parameter is identical with embodiment 59.
Embodiment 61: this embodiment is different with embodiment 59 or 60 is that the structure of electrostrictive polymer memory device is followed successively by anode, electroactive layer and negative electrode.Other parameter is identical with embodiment 59 or 60.
Anode is plated on the residuites such as glass or plastics through the vapor deposition mode and processes in this embodiment; Electroactive layer is through spin coating or inkjet technology film forming on anode; Negative electrode uses mask on electroactive layer, to form electrode through the mode of vacuum evaporation.
Embodiment 62: what this embodiment and embodiment 61 were different is that anode material is an indium oxide tin glass; Cathode material is aluminium or copper, and thickness is 600nm.Other parameter is identical with practical implementation 61.
Embodiment 63: the non-conjugated organic phosphine oxygen of this embodiment rare earth coordination polymer is as the application of the electroactive layer of electrostrictive polymer memory device, the P4 that the electrostrictive polymer memory device obtains with embodiment 45 1%Be electroactive layer, thickness is 40nm; Anode is an indium oxide tin glass; Cathode material is an aluminium, and thickness is 600nm.

Claims (9)

1. unconjugated organic phosphorus, oxide rare earth coordination polymer; It is characterized in that the unconjugated organic phosphorus, oxide rare earth coordination polymer is as monomer with polymerizable organic phosphine oxygen rare earth compounding and VCz; Obtain through free-radical polymerized, unconjugated organic phosphorus, oxide rare earth coordination polymer chemical structural formula is shown in (I):
Figure FSB00000568234300011
Wherein, n: m=1: 99～10: 90, m+n=100, m, n are positive integer; RE is a REE; Ar is carbazyl, di-p-methoxy-diphenylamine base and hexichol amido; R 1Be trifluoromethyl; R 2Be hydrogen; R 3Be thienyl.
2. unconjugated organic phosphorus, oxide rare earth coordination polymer according to claim 1; It is characterized in that the polymerizable organic phosphine oxygen rare earth compounding monomer in the unconjugated organic phosphorus, oxide rare earth coordination polymer is to be obtained by polymerizable organic phosphine oxygen compound neutral ligand, beta-diketon anion ligand and rare earth central metallic ions complex reaction, the chemical structural formula of polymerizable organic phosphine oxygen rare earth compounding is suc as formula shown in (II):
Figure FSB00000568234300012
3. unconjugated organic phosphorus, oxide rare earth coordination polymer according to claim 2 is characterized in that the RE in the polymerizable organic phosphine oxygen rare earth compounding monomer is lanthanum, cerium, praseodymium, promethium, samarium, europium, gadolinium, dysprosium, holmium, terbium, erbium, thulium, ytterbium or lutetium rare earth ion.
4. according to claim 2 or 3 described unconjugated organic phosphorus, oxide rare earth coordination polymers, the chemical structural formula that it is characterized in that polymerizable organic phosphine oxygen compound neutral ligand in the polymerizable organic phosphine oxygen rare earth compounding monomer is shown in (III):
Figure FSB00000568234300021
5. the preparation method of unconjugated organic phosphorus, oxide rare earth coordination polymer as claimed in claim 1; The preparation method who it is characterized in that the unconjugated organic phosphorus, oxide rare earth coordination polymer is: with polymerizable organic phosphine oxygen rare earth compounding and VCz is that 1: 1.3～100 ratio adds in the organic solvent in molar ratio; And then adding radical initiator; At inert gas atmosphere, 60～80 ℃ of following reaction 10～90h, behind sedimentation, separation, extraction, drying, desolventizing, promptly get the unconjugated organic phosphorus, oxide rare earth coordination polymer more then; Wherein organic solvent is THF or methylene dichloride; The ratio of VCz molar weight and organic solvent volume is 1mmol: 0.5～10mL; Radical initiator is azo-initiator or peroxide initiator, and the molar weight of radical initiator is 5% of polymerizable organic phosphine oxygen compound rare earth compounding and a VCz integral molar quantity.
6. the preparation method of unconjugated organic phosphorus, oxide rare earth coordination polymer according to claim 5; The preparation method who it is characterized in that polymerizable organic phosphine oxygen rare earth compounding used among the preparation method of unconjugated organic phosphorus, oxide rare earth coordination polymer is: three normal beta-diketons are dissolved in the organic solvent; Add the aqueous sodium hydroxide solution that contains three Equivalent Hydrogen sodium oxides again; Then behind reaction 15～30min under 60 ℃; Add again behind the rare earth soluble salt of monovalent at 60 ℃ of reaction 30～60min down, and then the polymerizable organic phosphine oxygen compound of monovalent is added in the previous reaction system, then 60～70 ℃ of reactions 2～8 hours down; Behind extraction, separation, drying, desolventizing, recrystallization gets polymerizable organic phosphine oxygen rare earth compounding more then; Wherein, the ratio of the molar weight of beta-diketon and organic solvent volume is 3mmol: 10mL, and organic solvent is alcohols, THF or methylene dichloride.
7. the preparation method of unconjugated organic phosphorus, oxide rare earth coordination polymer according to claim 6; The preparation method who it is characterized in that polymerizable organic phosphine oxygen compound used among the preparation method of polymerizable organic phosphine oxygen rare earth compounding realizes through following steps: one, under room temperature, alkaline system; With purifying to such an extent that vinyl benzyl replaces the Ar bromide behind Ar bromide and the vinyl chloride hybrid reaction 12～18h, wherein the mol ratio of Ar bromide and vinyl chloride is 1: 1～1.5; Two, the vinyl benzyl that step 1 is obtained replaces the Ar bromide and adds in the organic solvent after anhydrous and oxygen-free is handled, and stirring and dissolving gets mixed system, then mixed system is cooled to-78～0 ℃; Insulation adds n-Butyl Lithium afterreaction 1～2h again in mixed system, react 0.5～1h again after being warming up to room temperature then; And then mixed system is cooled to-78～0 ℃, insulation is after diethyl ether solution or the volumetric concentration that adds volumetric concentration again and be 50% diphenyl phosphine chloride is the tetrahydrofuran solution of 50% diphenyl phosphine chloride; Reaction 1～3h; Be warming up to room temperature afterreaction 8～24h again, purify and obtain the organic phosphine oxygen compound, wherein; Organic solvent is anhydrous diethyl ether or THF; The mol ratio that vinyl benzyl replaces Ar bromide and n-Butyl Lithium is 1: 2～2.5, and the ratio that vinyl benzyl replaces Ar bromide and organic solvent is 1mmol: 5mL, and the mol ratio that vinyl benzyl replaces Ar bromide and diphenyl phosphine chloride ether is 1: 1; Three, the organic phosphine oxygen compound that step 2 is obtained adds in the organic solvent, and stirring and dissolving adds ydrogen peroxide 50 again; And then react 2～4h under the room temperature, obtain polymerizable organic phosphine oxygen compound, wherein; Organic solvent is 1; 4-dioxane, methylene dichloride or chloroform, the ratio of organic phosphine oxygen compound and organic solvent are 1mmol: 5mL, organic phosphine oxygen compound and H 2O 2Mol ratio be 1: 1～1.5.
8. the application of unconjugated organic phosphorus, oxide rare earth coordination polymer as claimed in claim 1 is characterized in that the application of unconjugated organic phosphorus, oxide rare earth coordination polymer as the luminescent layer material or the luminescent layer dopant material of electroluminescent device.
9. the application of non-conjugated organic phosphine oxygen rare earth coordination polymer as claimed in claim 1 is characterized in that the application of unconjugated organic phosphorus, oxide rare earth coordination polymer as the electroactive layer of electrostrictive polymer memory device.
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