CN103524539B - Luminescent material Zn (phen) (HL) 2and preparation method thereof - Google Patents
Luminescent material Zn (phen) (HL) 2and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to luminescent material technical field, be specifically related to luminescent material Zn (phen) (HL)
2and preparation method thereof.The technical problem to be solved in the present invention is to provide a kind of luminescent material.Technical scheme of the present invention is emitting complexes Zn (phen) (HL1)
2, its molecular structure is as follows:
present invention also offers title complex Zn (phen) (HL)
2preparation method.The invention provides a kind of new blue emitting material.
Description
Technical field
The invention belongs to luminescent material technical field, be specifically related to luminescent material Zn (phen) (HL)
2and preparation method thereof.
Background technology
Metal-organic complex, have phosphor Stability Analysis of Structures, the advantage of long service life and the advantage such as luminous organic material high-luminous-efficiency, luminous spectrum bandwidth concurrently, the width of its photoluminescent band, wavelength (color) and intensity can by selecting the organic ligand of different metal ions, different structure and regulating by adding the methods such as other part formation multicomponent complex simultaneously.Tang in 1987 etc. use Metal-organic complex oxine aluminium (AlQ first
3) as luminescent layer prepared DC low-voltage drive high brightness luminescent device (OLED); Hamada in 1993 etc. have prepared as luminescent layer the luminescent device reaching application request with 10-hydroxy benzo quinoline beryllium.Subsequently, Metal-organic complex obtains the concern of various countries material supply section scholar as luminescent material, is the luminescent material that the class that is the most extensive, application forefront of research is at present excellent.
Metal-organic complex luminescent material has following several possible luminous mechanism: one, organic ligand: containing luminophore, after absorbing UV-light and visible ray, light emission directly can come from part, or and along with the charge transfer effect between metal or metal cluster; Two, metal ion: the illumination effect of transition metal ion is quenched because having azygous electronics, but lanthanide series metal, when close to organic luminophores, each ion in structure produces antenna effect, and fluorescence radiation intensity is strengthened greatly; Three, excited state complex compound: the pi-pi accumulation effect between contiguous conjugation organic ligand also can make to excite title complex luminous.As can be seen here, the selection of organic ligand and metal ion, also has the packed structures of crystal all to have impact to the luminescent properties of title complex.
In view of styryl or sub-styryl (-C
6h
4cH=CH-) be typical conjugation chromophoric group, the delocalizedπelectron system extended, the conductive performance of electronics can be improved and can be used as " passage " of photoelectron transfer, so the title complex that vinylbenzene fundamental mode organic ligand and metal ion are formed is the charge transfer emitter of a class uniqueness.
Metal-the luminous organic material in the past reported, mainly deposit deficiency both ways: (1) is Shortcomings in part selection, the conjugated degree of part is low, in general, the conjugated degree of part is larger, title complex conjugate planes and rigid structure degree larger, the luminous efficiency of title complex is higher.(2) stability is not high, can dissolve in water, ethanol, DMF (N, N '-dimethyl methane amide) equal solvent, or very easily weathering.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of luminescent material.
Technical scheme of the present invention is emitting complexes Zn (phen) (HL1)
2, its molecular structure is as follows:
Wherein, described title complex is from zinc salt, part H
2l sets out and is prepared from, and described part is a kind of polydentate ligand containing O, and the atom N in the carboxyl O in part and Ligands 1,10-phenanthroline (phen) and central atom Zn coordination form the pentacoordinate Metal-organic complex of following structure.
Present invention also offers title complex Zn (phen) (HL)
2preparation method, comprise the steps: adopt hydrothermal synthesis method, take raw material by following mol ratio: H
2l ︰ phen (1,10-phenanthroline) ︰ Xin Yan ︰ DMF ︰ H
2o=95 ~ 103 ︰ 91 ~ 111 ︰ 94 ~ 104 ︰ 23264 ~ 28556 ︰ 433333 ~ 455556, mixture stirs 0.5 ~ 3h, finally reacts 2 ~ 4 days under 75 ~ 85 ° of C in encloses container; After naturally cooling, filter, obtain yellow bulk crystals and be target product.
Preferably, H
2l, phen, zinc salt, DMF, H
2the mol ratio of O is 100 ︰ 100 ︰ 100 ︰ 2560 ︰ 44444.
Wherein, described zinc salt is Zn (NO
3)
26H
2o, ZnCl
2, Zn (O
2cCF
3), ZnBr
2, ZnO, ZnSO
47H
2o or Zn (O
3sCH
3).
Preferably, described zinc salt is ZnSO
47H
2o.
Preferably, described encloses container is the vial of band screw cap.
Preferably, the described reaction times is 3 days.
Preferably, described temperature of reaction is 80 DEG C.
Preferably, described yellow bulk crystals uses water, methanol wash, seasoning successively.
Beneficial effect of the present invention:
The title complex quite stable of the present invention's synthesis, is insoluble in water, ethanol, DMF (N, N ,-dimethyl formamide) equal solvent (except DMSO), and not easy-weathering, luminous efficiency is 0.075.The invention provides a kind of new blue emitting material, have better potential application prospect and fundamental research meaning.This Zn complex is more superior condition as novel fluorescence Development of Photo And Cathodoluminescent Materials place mat.The productive rate of the inventive method can reach 70.8% ~ 75.9%.
Accompanying drawing explanation
Fig. 1 H
2the structural formula of L
Fig. 2 Zn (phen) (HL)
2single crystal structure figure
Fig. 3 Zn complex [Zn (phen) (HL)
2] appearance of n
Fig. 4 crystal blue light-emitting (under 365nm ultra violet lamp)
The Solid fluorescene spectrum (, at 450nm, maximum excitation wavelength is at 373nm for maximum emission wavelength) of Fig. 5 title complex
Fig. 6 x-ray powder diffraction
Embodiment
Two H are comprised in the asymmetric cell of title complex
2l, a phen, a zine ion.Zine ion adopts hexa-coordinate mode, from two atom N (phen from chelating) and four O atoms (from two different H
2l) coordination.Part H
2two O atoms on the carboxyl of L one end are connected on zine ion in the mode of chelating, and the carboxyl oxygen atom of the other end has neither part nor lot in coordination.This material, after fluorescence experiments, finds there is very strong fluorescent emission (see Fig. 3,4) at 450nm place, becomes a kind of new blue emitting material, have better potential application prospect and good fundamental research meaning.
This complex crystal prepared by the present invention that takes a morsel, such as 0.1 ~ 0.2g crystal uses 50 ~ 100mL water, 50 ~ 100mL ethanol, 50 ~ 100mLDMF (N, N ,-dimethyl formamide) equal solvent (except DMSO) to dissolve respectively, finds indissoluble.Take a morsel crystal, such as 0.1g ~ 0.2g crystal, and open wide placement 10 ~ 20 days in air, title complex is faint yellow bulk crystals not yet, and not easy-weathering is described.
The H used in the present invention
2the preparation process reference [1] of L.
Part H selected by the present invention
2l conjugated degree is very large.H in reaction process
2l has sloughed a H atom, becomes the zinc ion coordination in HL-1 and zinc sulfate.The product obtained is with H
2l is the productive rate according to calculating.Namely according to H in reactant
2l and Zn (phen) (HL)
2mol ratio, convert and obtain Zn (phen) (HL) that should obtain in theory
2quality, then according to actual Zn (phen) (HL) that obtain
2quality, the ratio that the latter accounts for the former is productive rate.
In the present invention, X-ray diffraction analysis is carried out to final product, obtain its crystalline structure.And a series of sign is carried out to final product, and as ultimate analysis, infrared, fluorescence, x-ray powder diffraction.
The present invention also measured weres the luminous efficiency of products obtained therefrom, Quinine Sulphate Di HC is selected to measure as standard specimen, sample DMSO dissolves, UV, visible light tester and the coupling of fluorometric investigation instrument, used test instrument is UV, visible light testing tool is HITACHIUV1800, and fluorometric investigation instrument is HITACHIF-7000.
The preparation of embodiment 1 title complex of the present invention
35.0 milligrams of (0.095 mmole) H are added in 50mL glass beaker
2l, 18.0 milligrams of (0.091 mmole) phen, 27.1 milligrams of (0.094 mmole) ZnSO
4, 1.8mL (23.264 mmole) DMF, 7.8mL (433.333 mmole) H
2o, mixture stirs 0.5h, is then transferred to 20mL and is with in the vial of screw cap, react after 3 days under 80 ° of C, naturally cool to room temperature, observe light yellow crystal, be i.e. target product, it is filtered out from mother liquor, uses water, methanol wash successively, complete rear seasoning.
Product Zn (phen) (HL)
2in C, H, N element carry out ultimate analysis, calculated value (%): C, 66.43; H, 5.38; N, 2.77; Actually to record (%): C, 66.75; H, 4.99; N, 2.86.FT-IR(KBr,cm
-1):1635(m),1599(m),1555(s),1406(s),846(m),723(s)。Illustrate: elemental analysis value is recorded by Perkin-Elmer2400 elemental analyser; Infrared spectra is that the end is at 400 ~ 4000cm by NicoletImpact410FTIR spectrograph with KBr
-1record in scope.
X-ray diffraction analysis is carried out to the target product obtained, obtains its crystalline structure (see figure 2).Demonstrate each zine ion of this title complex and adopt hexa-coordinate mode, from two atom N (phen from chelating) and four O atoms (from two different parts) coordination.Two O atoms on the carboxyl of part one end are connected on zine ion in the mode of chelating, and the carboxyl oxygen atom of the other end has neither part nor lot in coordination.
Product is recorded to target product RF-5301PC luminoscope and has emission maximum (under 373nm maximum excitation) at 450nm place; Result shows that this invention product is a kind of blue light emitting material (see figure 5).Carry out powdery diffractometry test with Shimadzu XRD-6100 type X-ray diffraction instrument, the peak of test collection of illustrative plates well mates with the peak energy of the collection of illustrative plates through Mercury software simulation, illustrates that this crystal is target product, and the higher (see figure 6) of sample purity.
By the present embodiment repeatedly, actual production obtains Zn (phen) (HL)
2quality remain on 34.6 ~ 37.1mg, calculate as productive rate 74.5% ~ 80%.
The preparation of embodiment 2 title complex of the present invention
36.8 milligrams of (0.1 mmole) H are added in 50mL glass beaker
2l, 19.8 milligrams of (0.1 mmole) phen, 28.8 milligrams of (0.1 mmole) ZnSO
4, 2mL (25.960 mmole) DMF, 8mL (444.444 mmole) H
2o, mixture stirs 0.5h, is then transferred to 20mL and is with in the vial of screw cap, react after 3 days under 80 ° of C, naturally cool to room temperature, observe light yellow crystal, be i.e. target product, it is filtered out from mother liquor, uses water, methanol wash successively, complete rear seasoning.
Ultimate analysis, infrared, fluorescence, x-ray powder diffraction sign are carried out to product, obtains data similar to embodiment 1.The crystalline structure that explanation embodiment 2 obtains does not change and the purer (see figure 6) of product, and performance is also the (see figure 5) that changes.
By the present embodiment repeatedly, obtain Zn (phen) (HL) according to actual production
2quality, calculate as productive rate 70.8% ~ 75.9%.
The preparation of embodiment 3 title complex of the present invention
37.9 milligrams of (0.103 mmole) H are added in 50mL glass beaker
2l, 22.0 milligrams of (0.111 mmole) phen, 30.0 milligrams of (0.104 mmole) ZnSO
4, 2.2mL (28.556 mmole) DMF, 8.2mL (455.556 mmole) H
2o, mixture stirs 0.5h, is then transferred to 20mL and is with in the vial of screw cap, react after 3 days under 80 ° of C, naturally cool to room temperature, observe light yellow crystal, be i.e. target product, it is filtered out from mother liquor, uses water, methanol wash successively, complete rear seasoning.
Ultimate analysis, infrared, fluorescence, x-ray powder diffraction sign are carried out to product, obtains data similar to embodiment 1.Illustrate that structure does not also change and the purer (see figure 6) of product with embodiment 3 obtained crystal, performance does not change (see figure 5) yet.
By the present embodiment repeatedly, obtain Zn (phen) (HL) according to actual production
2quality, calculate as productive rate 68.7% ~ 73.7%.
From Fig. 4 and Fig. 5, obtained Zn complex Zn (phen) (HL)
2, the feed molar proportioning that takes is: H
2l1 ︰ phen (1,10-phenanthroline) ︰ ZnSO4 ︰ DMF ︰ H
2o=95 ~ 103 ︰ 91 ~ 111 ︰ 94 ~ 104 ︰ 23264 ~ 28556 ︰ 433333 ~ 455556 is comparatively suitable; Zn complex Zn (phen) (HL) of gained
2product is purer, and fluorescence maximum emission wavelength, 450nm place (under 373nm wavelength excites), illustrates that this title complex sends out stronger blue light, likely becomes novel fluorescence luminescent material.
Reference:
[1]Koepp,E.;
F.Perkin-Synthesemit
Synthesis.1987,(2),177-178。
Claims (19)
1. emitting complexes Zn (phen) (HL)
2, its molecular structure is as follows:
2. title complex as claimed in claim 1, is characterized in that: described title complex is from zinc salt, part H
2l sets out and is prepared from, and described part is a kind of polydentate ligand containing O, and the atom N in the carboxyl O in part and Ligands 1,10-phenanthroline (phen) and central atom Zn coordination form the pentacoordinate Metal-organic complex of following structure; H
2the structural formula of L is as follows:
3. title complex Zn (phen) (HL) described in claim 1 or 2
2preparation method, it is characterized in that: comprise the steps: adopt hydrothermal synthesis method, take raw material by following mol ratio: H
2l ︰ phen (1,10-phenanthroline) ︰ Xin Yan ︰ DMF ︰ H
2o=95 ~ 103 ︰ 91 ~ 111 ︰ 94 ~ 104 ︰ 23264 ~ 28556 ︰ 433333 ~ 455556, mixture stirs 0.5 ~ 3h, finally reacts 2 ~ 4 days at 75 ~ 85 DEG C in encloses container; After naturally cooling, filter, obtain yellow bulk crystals and be target product; Described H
2the structural formula of L is as follows:
4. preparation method as claimed in claim 3, is characterized in that: described zinc salt is Zn (NO
3)
26H
2o, ZnCl
2, Zn (O
2cCF
3), ZnBr
2, ZnSO
47H
2o or Zn (O
3sCH
3).
5. preparation method as claimed in claim 4, is characterized in that: described zinc salt is ZnSO
47H
2o.
6. the preparation method as described in claim 3 or 4, is characterized in that: described encloses container is the vial of band screw cap.
7. preparation method as claimed in claim 5, is characterized in that: described encloses container is the vial of band screw cap.
8. the preparation method as described in claim 3 or 4, is characterized in that: the described reaction times is 3 days.
9. preparation method as claimed in claim 5, is characterized in that: the described reaction times is 3 days.
10. preparation method as claimed in claim 6, is characterized in that: the described reaction times is 3 days.
11. preparation methods as described in claim 3 or 4, is characterized in that: described temperature of reaction is 80 DEG C.
12. preparation methods as claimed in claim 5, is characterized in that: described temperature of reaction is 80 DEG C.
13. preparation methods as claimed in claim 6, is characterized in that: described temperature of reaction is 80 DEG C.
14. preparation methods as claimed in claim 8, is characterized in that: described temperature of reaction is 80 DEG C.
15. preparation methods as described in claim 3 or 4, is characterized in that: described yellow bulk crystals uses water, methanol wash, seasoning successively.
16. preparation methods as claimed in claim 5, is characterized in that: described yellow bulk crystals uses water, methanol wash, seasoning successively.
17. preparation methods as claimed in claim 6, is characterized in that: described yellow bulk crystals uses water, methanol wash, seasoning successively.
18. preparation methods as claimed in claim 8, is characterized in that: described yellow bulk crystals uses water, methanol wash, seasoning successively.
19. preparation methods as claimed in claim 11, is characterized in that: described yellow bulk crystals uses water, methanol wash, seasoning successively.
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| CN105885827B (en) * | 2015-08-07 | 2018-04-10 | 重庆师范大学 | Fluorescent red-orange material zinc coordination polymer [Zn (HL) (HBPEP)]nAnd its synthetic method |
| CN106279217B (en) * | 2016-07-18 | 2018-02-06 | 重庆师范大学 | Cadmium organic supermolecular solid [Cd (ppa) (bpe)]nAnd preparation method |
| CN106349260A (en) * | 2016-08-29 | 2017-01-25 | 重庆师范大学 | Greenyellow fluorescent supermolecule material including aryl vinyl and preparing method and application of greenyellow fluorescent supermolecule material |
| CN106565756B (en) * | 2016-11-10 | 2018-08-14 | 重庆师范大学 | A kind of copper coordination polymer [Cu2(Hntb)2(bpeb)] and the preparation method and application thereof |
| CN110628037B (en) * | 2019-09-12 | 2021-10-26 | 重庆师范大学 | Yellow fluorescent mixed manganese supramolecular polymer and preparation method and application thereof |
| CN112094283B (en) * | 2020-10-10 | 2022-09-09 | 宁波大学 | Aninorinone zinc complex blue fluorescent material and preparation method thereof |
| CN114149453B (en) * | 2021-12-16 | 2023-07-28 | 江西省科学院应用化学研究所 | Zinc-based hybrid material for blue light emission and preparation method thereof |
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