CN105885827A - Orange red fluorescent material zinc coordination polymer [Zn(HL)(HBPEP)] and synthesizing method thereof - Google Patents
Orange red fluorescent material zinc coordination polymer [Zn(HL)(HBPEP)] and synthesizing method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of light-emitting materials and particularly relates to an orange red fluorescent material zinc coordination polymer [Zn(HL)(HBPEP)] and a synthesizing method thereof. The structure of the orange red fluorescent material zinc coordination polymer [Zn(HL)(HBPEP)] is shown in the description. The invention further provides the synthesis method of the coordination polymer. The coordination polymer is prepared from zinc nitrate, ligand H4L and BPEP. The novel orange red fluorescent material is provided and has high heat stability.
Description
Technical field
The invention belongs to luminescent material technical field, be specifically related to fluorescent red-orange material zinc coordination polymer [Zn (HL) (HBPEP)] and synthetic method thereof.
Background technology
Fluorescence probe is one of life science the most representational molecular imaging means, has the advantages such as highly sensitive, radiationless.The agricultural film that light conversion agent mixes is one of important goods of modern high technology agricultural needs, current light conversion agent is developed based on strategic resource rare earth metal, and the finiteness of rare earth resources and high cost make the light altering film for agriculture application in high technological aqriculture field be limited by very large.Therefore, research and development have and turn the important front edge problem that the novel fluorescent material of light function is above-mentioned two big fields.
Since within 1987, being prepared for high brightness luminescent device (OLED) with 8-hydroxyquinoline aluminum (AlQ3), Metal-organic complex is the fluorescent material that the class the most extensive, application forefront of research at present is excellent.Wherein transition metal-organic coordination compound is important luminescent material type, it has phosphor Stability Analysis of Structures, the advantage of length in service life and the advantage such as luminous organic material high-luminous-efficiency, luminous spectrum bandwidth concurrently, and the width of its photoluminescent band, wavelength (color) and intensity by selecting different metal ion, the organic ligands of different structure and can be adjusted by adding the methods such as other part formation multicomponent complex simultaneously.Such material includes the coordination compound (including coordination polymer) that the metal ions such as Re (I), Ru (II), Pt (II), Ir (III), Cu (I) and Zn (II) are formed with multifunctional organic component.Developing novel redness or fluorescent orange Metal-organic complex is Coordinative Chemistry field study hotspot over nearly 10 years, main policies is is raw material with the salt of noble metal or rare earth metal (such as Ru, Pt, Eu) and polyfunctional organic ligand (such as beta-dicarbonyl ketone, organic polycarboxylic acid, bipyridyl, porphyrin etc.) is coordinated.
Owing to normal transition metallic zinc (Zn) and salt thereof are cheap and easy to get, zinc ion coordination ability is strong, gained complex structure is various and good stability, the always important directions of fluorescent material research field, up to now, synthesize ten hundreds of Zn-organic coordination compounds, but overwhelming majority zinc-organic coordination compound launches blue or green fluorescence, therefore prepare novel redness or fluorescent orange solid material from zinc salt cheap and easy to get and Organic Ingredients, be one of current functional material chemical field problem with challenge.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of fluorescent red-orange material.
The technical scheme is that fluorescent red-orange zinc coordination polymer [Zn (HL) (HBPEP)], its structure is as follows:Wherein HL is organic carboxyl acid H4L sloughs the component after 3 carboxyl hydrogen atoms, H4The structural formula of L isHBPEP be containing n-donor ligand BPEP monoprotonated after component, the structural formula of BPEP is
Concrete, described coordination polymer is by zinc nitrate, part H4L and BPEP sets out and is prepared from, described part H4L is a kind of multidentate ligand containing O, and described part BPEP is a kind of bidentate ligand containing stibazole, the carboxyl O in part and the four-coordination metal-organic coordination polymer of pyridine N and the central atom Zn coordination following structure of formation.
Present invention also offers the synthetic method of coordination polymer [Zn (HL) (HBPEP)], comprise the steps: to use solvent process for thermosynthesizing, weigh raw material by following mol ratio: H4L BPEP Zn (NO3)2H2O CH3CN=27～33 16～20 43～47 7933～8,733 380～3936, by raw material mix and blend 0.5～3h, reacts 3～5 days in hermetic container at 100～120 DEG C；After natural cooling, filter, obtain orange bulk crystals and be target product；Wherein, H4The structural formula of L isThe structural formula of BPEP is
Preferably, H4L BPEP Zn (NO3)2H2O CH3The mol ratio of CN is 30 18 45 8,333 3658.
Preferably, described hermetic container is reactor.
Preferably, the described response time is 4 days.
Preferably, described reaction temperature is 110 DEG C.
Preferably, described orange bulk crystals is successively with water, acetonitrile washing, natural drying.
Beneficial effects of the present invention:
Part selected by the present invention, containing styryl such conjugation group, forms big π key, be conducive to the part absorption to ultraviolet light, the energy transfer efficiency of part-zinc ion is high, and above-mentioned advantage is conducive to part sensitization zinc ion, causes zinc ion to send the orange-red light of feature.Containing aerobic and nitrogen dentate in part, selecting zinc nitrate as the source of zinc ion, beneficially oxygen, nitrogen-atoms is coordinated with central ion zinc, forms a kind of novel fluorescent red-orange material, has good potential application foreground and basic research meaning.This Zn complex has higher heat stability, and 200 DEG C start to decompose (Fig. 5), develop the more superior condition of place mat for novel fluorescent material.The inventive method is simple to operate, and productivity can reach 50.4%～63.0%.
Accompanying drawing explanation
Fig. 1 H4The structural formula of L
The structural formula of Fig. 2 BPEP
The coordinate crystal structure of Fig. 3 [Zn (HL) (HBPEP)] metallic zinc ion
Fig. 4 crystal sends out fluorescent red-orange photo (under 365 ultra violet lamps)
Thermogravimetric curve (the N of Fig. 5 coordination compound2Atmosphere；Abscissa temperature；Vertical coordinate percent weight loss)
Solid fluorescence emission spectrum (the abscissa wavelength of Fig. 6 coordination compound；Vertical coordinate absorption intensity)
Fig. 7 X-ray powder diffraction pattern (abscissa angle of diffraction；Vertical coordinate absorption intensity)
Detailed description of the invention
In the dissymmetrical structure unit of coordination compound, include the HL of part deprotonation3-Part and monoprotonated HBPEP part.Each zinc ion uses the mode of four-coordination, respectively with three HL3-Carboxyl oxygen on part and the coordination of the nitrogen-atoms on a HBPEP.This material, after fluorescence experiments, finds there is strong fluorescent emission (see Fig. 4 and Fig. 6) at 614nm, becomes a kind of new fluorescent red-orange material.
Part H selected by the present invention4The conjugated degree of L (structural formula is shown in Fig. 1) and BPEP (structural formula is shown in Fig. 2) is bigger.H in course of reaction4L has sloughed 3 H atom, becomes HL3-, and and zinc ion coordination.The product obtained is with H4L is according to calculating productivity, i.e. according to H in reactant4L and the mol ratio of [Zn (HL) (HBPEP)], calculate the quality of [Zn (HL) (HBPEP)] that should obtain in theory, further according to [Zn (HL) (the HBPEP)] quality actually obtained, the latter accounts for the former ratio and is productivity.
H used in the present invention4L is purchased from Shanghai Jia Chen Chemical Co., Ltd.；The preparation process list of references [1] of BPEP.
End product is carried out X-ray single crystal diffraction analysis by the present invention, obtains its crystal structure；And end product is carried out a series of sign, such as elementary analysis, infrared, fluorescence, X-ray powder diffraction.
The preparation of embodiment 1 coordination compound of the present invention
Raw material is weighed: H by following mol ratio4L BPEP Zn (NO3)2H2O CH3CN=27 16 43 7,933 3380 is as in 50mL glass beaker, mixture 0.5 hour (h) of stirring, then it is transferred in 25mL reactor, after reacting 3 days at 100 DEG C, naturally cool to room temperature, it was observed that orange crystal, it is target product, it is filtered out from mother solution, successively with water, acetonitrile washing, complete rear natural drying.
C in product [Zn (HL) (HBPEP)], H, N element carry out elementary analysis, value of calculation (%): C, and 65.45；H,3.64；N,3.64.Actually measured (%): C, 65.21；H,3.53；N,3.57.FT-IR (KBr, cm-1): 3306 (w), 3199 (w), 3077 (w), 1672 (m), 1607 (vs), 1498 (m), 1395 (vs), 1236 (s), 1157 (m), 880 (m).Illustrate: elemental analysis value is recorded by Perkin-Elmer2400 elemental analyser；External spectrum by Nicolet Impact 410FTIR spectrogrph with KBr the end of at 400-4000cm-1In the range of record.
The target product obtained is carried out X-ray single crystal diffraction analysis, it is thus achieved that its crystal structure (see Fig. 3).Demonstrate each zinc ion of this coordination compound and use four-coordination mode, three HL3-Three oxygen atoms on carboxylate radical are connected with zinc ion with a nitrogen-atoms on HBPEP.
Target product RF-5310IPC luminoscope is recorded product at 614nm, has emission maximum (under 550nm excites): result shows that this invention product is a kind of fluorescent red-orange material (see Fig. 4 and Fig. 6).Carrying out powder diffraction test with Shimadzu XRD-6100 type x-ray diffractometer, the peak of test collection of illustrative plates well mates with the peak energy of the collection of illustrative plates simulated through mercury software, illustrates that this crystal is target product, and sample purity higher (see Fig. 7).
By the present embodiment repeatedly, actual production obtains the quality of [Zn (HL) (HBPEP)] and is maintained at 50.8～60.3mg, is calculated as productivity 50.5%～60.3%.
The preparation of embodiment 2 coordination compound of the present invention
Raw material is weighed: H by following mol ratio4L BPEP Zn (NO3)2H2O CH3CN=30 18 45 8,333 3658 is as in 50mL glass beaker, mixture 2 hours (h) of stirring, then it is transferred in 25mL reactor, after reacting three days at 110 DEG C, naturally cool to room temperature, it was observed that clear crystal, i.e. target product, it is filtered out from mother solution, successively with water, acetonitrile washing, complete rear natural drying.
Product is carried out elementary analysis, infrared, fluorescence, X-ray powder diffraction sign, obtains data similar to Example 1.The crystal structure that explanation embodiment 2 prepares does not changes and product purer (see Fig. 7), and performance does not changes (see Fig. 6) yet.
By the present embodiment repeatedly, obtaining the quality 60.5～72.6 of [Zn (HL) (HBPEP)] according to actual production, calculated yield is 52.5%～63%.
The preparation of embodiment 3 coordination compound of the present invention
Raw material is weighed: H by following mol ratio4L BPEP Zn (NO3)2H2O:CH3CN=33 20 47 8,733 3936 is as in 50mL glass beaker, mixture stirring 3h, then it is transferred in 25mL reactor, after reacting three days under 120 degree, naturally cool to room temperature, it was observed that orange crystal, i.e. target product, it is filtered out from mother solution, successively with water, acetonitrile washing, complete rear natural drying.
Product is carried out elementary analysis, infrared, fluorescence, X-ray powder diffraction sign, obtains data similar to Example 1.The crystal structure that explanation embodiment 3 prepares does not changes and product purer (see Fig. 7), and performance does not changes (see Fig. 6) yet.
By the present embodiment repeatedly, obtaining the quality 60.5～72.6 of [Zn (HL) (HBPEP)] according to actual production, calculated yield is 52.5%～63%.
From Fig. 6 and Fig. 7, preparing Zn complex [Zn (HL) (HBPEP)], weighed feed molar proportioning is H4L BPEP Zn (NO3)2H2O CH3CN=30 18 45 8,333 3658 is the most suitable, response time be 3-5 days the most suitable: the Zn complex [Zn (HL) (HBPEP)] of gained is purer, fluorescence maximum emission wavelength at 614nm (under 550nm wavelength excites), illustrate that this coordination compound sends out stronger fluorescent red-orange, be a kind of novel fluorescent material.
List of references:
[1]William S.Wadsworth,William D.Emmons.The Utility of Phosphonate Carbanions in Olefin Synthesis.J.Am.Chem.Soc.,1961,83(7),1733–1738.
Claims (8)
1. fluorescent red-orange zinc coordination polymer [Zn (HL) (HBPEP)], its structure is as follows:Wherein HL is organic
Carboxylic acid H4L sloughs the component after 3 carboxyl hydrogen atoms, H4The structural formula of L isHBPEP
Be containing n-donor ligand BPEP monoprotonated after component, the structural formula of BPEP is
2. coordination polymer as claimed in claim 1, it is characterised in that: by zinc nitrate, part H4L and the BPEP system of setting out
For forming, described part H4L is a kind of multidentate ligand containing O, and described part BPEP is a kind of double containing stibazole
Tooth part, the carboxyl O in part and the four-coordination metal-organic coordination polymer of pyridine N and central atom Zn coordination formation.
3. the synthetic method of zinc coordination polymer described in claim 1 or 2 [Zn (HL) (HBPEP)], it is characterised in that: include
Following steps: use solvent process for thermosynthesizing, weigh raw material by following mol ratio: H4L BPEP Zn (NO3)2H2O
CH3CN=27～33 16～20 43～47 7933～8,733 380～3936, by raw material mix and blend 0.5～3h,
React 3～5 days at 100～120 DEG C in hermetic container；After natural cooling, filter, obtain orange bulk crystals and be mesh
Mark product；Wherein, H4The structural formula of L isThe structural formula of BPEP is
4. method as claimed in claim 3, it is characterised in that: H4L BPEP Zn (NO3)2H2O CH3CN rubs
Your ratio is 30 18 45 8,333 3658.
5. the method as described in claim 3 or 4, it is characterised in that: described hermetic container is reactor.
6. the method as described in any one of claim 3～5, it is characterised in that: the described response time is 4 days.
7. the method as described in any one of claim 3～6, it is characterised in that: described reaction temperature is 110 DEG C.
8. the method as described in any one of claim 3～7, it is characterised in that: described orange bulk crystals successively with water,
Acetonitrile washs, natural drying.
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| CN106854175A (en) * | 2016-12-14 | 2017-06-16 | 重庆师范大学 | Terpyridyl zinc benzoate complex and preparation condition |
| CN110551291A (en) * | 2019-09-06 | 2019-12-10 | 重庆师范大学 | Porous interpenetrating zinc-organic supramolecular polymer and preparation method and application thereof |
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| CN115785467A (en) * | 2022-11-28 | 2023-03-14 | 重庆师范大学 | Triple interpenetrating binuclear Zn 2 MOF material, preparation method thereof and application of MOF material in preparation of orange yellow LED device |
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| CN106854175A (en) * | 2016-12-14 | 2017-06-16 | 重庆师范大学 | Terpyridyl zinc benzoate complex and preparation condition |
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| CN110818907A (en) * | 2018-11-26 | 2020-02-21 | 河北民族师范学院 | Zinc coordination polymer containing polycarboxylic acid and multi-nitrogen dual ligand and preparation method thereof |
| CN110818907B (en) * | 2018-11-26 | 2021-10-01 | 河北民族师范学院 | Zinc coordination polymer containing polycarboxylic acid and multi-nitrogen dual ligand and preparation method thereof |
| CN110551291A (en) * | 2019-09-06 | 2019-12-10 | 重庆师范大学 | Porous interpenetrating zinc-organic supramolecular polymer and preparation method and application thereof |
| CN110551291B (en) * | 2019-09-06 | 2021-07-13 | 重庆师范大学 | Porous interpenetrating zinc-organic supramolecular polymer and preparation method and application thereof |
| CN115785467A (en) * | 2022-11-28 | 2023-03-14 | 重庆师范大学 | Triple interpenetrating binuclear Zn 2 MOF material, preparation method thereof and application of MOF material in preparation of orange yellow LED device |
| CN115785467B (en) * | 2022-11-28 | 2023-08-29 | 重庆师范大学 | Triple interpenetrating dinuclear Zn 2 MOF material, preparation method thereof and application of MOF material in preparation of orange-yellow light LED device |
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