CN105885827B - Fluorescent red-orange material zinc coordination polymer [Zn (HL) (HBPEP)]nAnd its synthetic method - Google Patents
Fluorescent red-orange material zinc coordination polymer [Zn (HL) (HBPEP)]nAnd its synthetic method Download PDFInfo
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Abstract
The invention belongs to luminescent material technical field, and in particular to fluorescent red-orange zinc coordination polymer [Zn (HL) (HBPEP)]nAnd its synthetic method.The invention discloses fluorescent red-orange zinc coordination polymerization [Zn (HL) (HBPEP)]n, monomer structure is as follows：Present invention also offers the synthetic method of the coordination polymer, using solvent process for thermosynthesizing by zinc nitrate, part H4L and BPEP, which sets out, to be prepared.The invention provides a kind of new fluorescent red-orange material, there is higher heat endurance.
Description
Technical field
The invention belongs to luminescent material technical field, and in particular to fluorescent red-orange material zinc coordination polymer [Zn (HL)
(HBPEP)]nAnd its synthetic method.
Background technology
Fluorescence probe is one of most representational molecular imaging means of life science, have high sensitivity,
The advantages that radiationless.The agricultural film that light conversion agent mixes is one of important goods of modern high technology agricultural needs, and current turns
Photo etching is developed based on strategic resource rare earth metal, and the finiteness of rare earth resources and high cost make light altering film for agriculture in high-tech
The application of skill agriculture field is limited by very large.Therefore, it is above-mentioned two that researching and developing, which has the novel fluorescent material for turning light function,
The important front edge problem in big field.
Since 1987 are prepared for high brightness luminescent device (OLED) with 8-hydroxyquinoline aluminium (AlQ3), metal-organic
Complex is current studies most extensively, using a kind of excellent fluorescent material of forefront.Wherein transition metal-organic coordination compound
It is important luminescent material type, the advantages of it has phosphor Stability Analysis of Structures concurrently, service life is long and organic light emission
The advantages that material high-luminous-efficiency, luminous spectrum bandwidth, while the width of its photoluminescent band, wavelength (color) and intensity can pass through
Select different metal ions, the organic ligand of different structure and by adding the methods of other parts form multicomponent complex
To be adjusted.Such material include the metal ion such as Re (I), Ru (II), Pt (II), Ir (III), Cu (I) and Zn (II) with
The complex (including coordination polymer) that multifunctional organic component is formed.Develop new red or fluorescent orange metal-organic
Complex is the study hotspot of field of coordinative chemistry in the past 10 years, main policies be with noble metal or rare earth metal (such as Ru, Pt,
Eu salt) is that raw material is coordinated with polyfunctional organic ligand (such as beta-dicarbonyl ketone, organic polycarboxylic acid, bipyridyl, porphyrin).
Because normal transition metallic zinc (Zn) and its salt are cheap and easy to get, zinc ion coordination ability is strong, gained complex structure
Various and stability is good, is always the important directions of fluorescent material research field, so far, has synthesized ten hundreds of
Zn- organic coordination compounds, but most zinc-organic coordination compound transmitting blueness or green fluorescence, therefore from zinc cheap and easy to get
Salt and Organic Ingredients, which set out, prepares new red or fluorescent orange solid material, is that current functional material chemical field has and chosen
One of problem of war.
The content 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)]n, monomer structure is such as
Under：Wherein HL is
Organic carboxyl acid H4L sloughs the component after 3 carboxyl hydrogen atoms, H4L structural formula is
HBPEP is the component after containing n-donor ligand BPEP monoprotonated, and BPEP structural formula is
Specifically, described coordination polymer is by zinc nitrate, part H4L and BPEP, which sets out, to be prepared, the part H4L
It is a kind of multidentate ligand containing O, the part BPEP is a kind of bidentate ligand containing stibazole, the carboxyl O in part
The four-coordination metal-organic coordination polymer to form following structure is coordinated with pyridine N and central atom Zn.
Present invention also offers coordination polymer [Zn (HL) (HBPEP)]nSynthetic method, comprise the following steps：Using
Solvent process for thermosynthesizing, raw material is weighed by following mol ratio：H4L ︰ BPEP ︰ Zn (NO3)2︰ H2O ︰ CH3The ︰ of CN=27~33 16~
The ︰ 380~3936 of 20 ︰, 43~47 ︰ 7933~8733, raw material is mixed into 0.5~3h, at 100~120 DEG C in closed container
Lower reaction 3~5 days；After natural cooling, filtering, it is target product to obtain orange bulk crystals；Wherein, H4L structural formula isBPEP structural formula is
Preferably, H4L ︰ BPEP ︰ Zn (NO3)2︰ H2O ︰ CH3CN mol ratio is the ︰ 3658 of 30 ︰, 18 ︰, 45 ︰ 8333.
Preferably, described closed container is reactor.
Preferably, the described reaction time is 4 days.
Preferably, described reaction temperature is 110 DEG C.
Preferably, described orange bulk crystals are washed with water, acetonitrile successively, are spontaneously dried.
Beneficial effects of the present invention：
Part selected by the present invention, containing group is conjugated as styryl, big pi bond is formed, is advantageous to part pair
The absorption of ultraviolet light, the energy transfer efficiency of part-zinc ion is high, and above-mentioned advantage is advantageous to part sensitization zinc ion, causes zinc
Ion sends the orange-red light of feature.Containing aerobic and nitrogen dentate in part, from source of the zinc nitrate as zinc ion, favorably
Be coordinated in oxygen, nitrogen-atoms and central ion zinc, form a kind of new fluorescent red-orange material, have good potential application foreground and
Basic research meaning.This Zn complex has higher heat endurance, and 200 DEG C start to decompose (Fig. 5), are sent out for novel fluorescent material
Expand and padded more superior condition.The inventive method is simple to operate, and yield can reach 50.4%~63.0%.
Brief description of the drawings
Fig. 1 H4L structural formula
Fig. 2 BPEP structural formula
Fig. 3 [Zn (HL) (HBPEP)]nThe coordinate crystal structure of metal zinc ion
Fig. 4 crystal hair fluorescent red-orange photo (under 365 ultra violet lamps)
Thermogravimetric curve (the N of Fig. 5 complexs2Atmosphere；Abscissa-temperature；Ordinate-percent weight loss)
Solid fluorescence emission spectrum (the abscissa-wavelength of Fig. 6 complexs；Ordinate-absorption intensity)
Fig. 7 X-ray powder diffractions style (abscissa-angle of diffraction；Ordinate-absorption intensity)
Embodiment
In the dissymmetrical structure unit of complex, include the HL of part deprotonation3-Part and monoprotonated HBPEP match somebody with somebody
Body.Each zinc ion by the way of four-coordination, respectively with three HL3-The nitrogen on carboxyl oxygen and a HBPEP on part
Atomic coordinate.The material finds there is strong fluorescent emission (see Fig. 4 and Fig. 6) at 614nm after fluorescence experiments, turns into a kind of
New fluorescent red-orange material.
Part H selected by the present invention4L (structural formula is shown in Fig. 1) and BPEP (structural formula is shown in Fig. 2) conjugated degree are larger.
H during the course of the reaction4L has sloughed 3 H atoms, becomes HL3-, and and zinc ion coordination.Obtained product is with H4L is according to meter
Yield is calculated, i.e., according to H in reactant4L and [Zn (HL) (HBPEP)]nMol ratio, calculate [the Zn (HL) that should be obtained in theory
(HBPEP)] n quality, further according to [Zn (HL) (HBPEP)] actually obtainednQuality, it is to produce that the latter, which accounts for the former ratio,
Rate.
H used in the present invention4L is purchased from Shanghai Jia Chen Chemical Co., Ltd.s；BPEP preparation process bibliography
[1]。
X-ray single crystal diffraction analysis is carried out to final product in the present invention, obtains its crystal structure；And to final product
A series of signs are carried out, such as elementary analysis, infrared, fluorescence, X-ray powder diffraction.
The preparation of 1 complex of the present invention of embodiment
Raw material is weighed by following mol ratio：H4L ︰ BPEP ︰ Zn (NO3)2︰ H2O ︰ CH3The ︰ 3380 of 16 ︰ of CN=27 ︰, 43 ︰ 7933
As in 50mL glass beakers, mixture stirs 0.5 hour (h), is then transferred in 25mL reactors, is reacted at 100 DEG C
After 3 days, room temperature is naturally cooled to, it was observed that orange crystal, as target product, it is filtered out from mother liquor, used successively
Water, acetonitrile washing, are spontaneously dried after complete.
Product [Zn (HL) (HBPEP)]nIn C, H, N element carry out elementary analysis, calculated value (%)：C,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).Explanation：Member
Plain assay value is measured by Perkin-Elmer2400 elemental analysers；External spectrum is by Nicolet Impact 410FTIR spectrum
Instrument is bottom in 400-4000cm using KBr-1In the range of measure.
X-ray single crystal diffraction analysis is carried out to obtained target product, obtains its crystal structure (see Fig. 3).Demonstrate this
The each zinc ion of complex uses four-coordination mode, three HL3-A nitrogen original on three oxygen atoms and HBPEP on carboxylate radical
Son is connected with zinc ion.
Measure product with RF-5310IPC luminoscopes to target product has emission maximum (to be excited in 550nm at 614nm
Under)：As a result it is a kind of fluorescent red-orange material to show this invention product (see Fig. 4 and Fig. 6).With Shimadzu XRD-6100 type X-rays
Diffractometer carries out powder diffraction test, and the peak energy for testing collection of illustrative plates of the peak of collection of illustrative plates with being simulated through mercury softwares matches well,
It is target product to illustrate this crystal, and sample purity is higher (see Fig. 7).
By the present embodiment repeatedly, actual production obtains [Zn (HL) (HBPEP)]nQuality be maintained at 50.8~
60.3mg, it is calculated as yield 50.5%~60.3%.
The preparation of 2 complex of the present invention of embodiment
Raw material is weighed by following mol ratio：H4L ︰ BPEP ︰ Zn (NO3)2︰ H2O ︰ CH3The ︰ 3658 of 18 ︰ of CN=30 ︰, 45 ︰ 8333
As in 50mL glass beakers, mixture stirs 2 hours (h), is then transferred in 25mL reactors, reacts three at 110 DEG C
After it, naturally cool to room temperature, it was observed that clear crystal, i.e. target product, it is filtered out from mother liquor, successively with water,
Acetonitrile washs, and is spontaneously dried after complete.
Elementary analysis, infrared, fluorescence, X-ray powder diffraction sign are carried out to product, obtains data and the phase of embodiment 1
Seemingly.Explanation crystal structure made from embodiment 2 does not change and product is purer (see Fig. 7), performance also do not change (see
Fig. 6).
By the present embodiment repeatedly, obtained [Zn (HL) (HBPEP)] according to actual productionnQuality 60.5~72.6,
Calculated yield is 52.5%~63%.
The preparation of 3 complex of the present invention of embodiment
Raw material is weighed by following mol ratio：H4L ︰ BPEP ︰ Zn (NO3)2︰ H2O:CH3The ︰ 3936 of 20 ︰ of CN=33 ︰, 47 ︰ 8733
As in 50mL glass beakers, mixture stirring 3h, then it is transferred in 25mL reactors, after being reacted three days under 120 degree, from
Room temperature so is cooled to, it was observed that orange crystal, i.e. target product, it is filtered out from mother liquor, washed successively with water, acetonitrile
Wash, spontaneously dried after complete.
Elementary analysis, infrared, fluorescence, X-ray powder diffraction sign are carried out to product, obtains data and the phase of embodiment 1
Seemingly.Explanation crystal structure made from embodiment 3 does not change and product is purer (see Fig. 7), performance also do not change (see
Fig. 6).
By the present embodiment repeatedly, obtained [Zn (HL) (HBPEP)] according to actual productionnQuality 60.5~72.6,
Calculated yield is 52.5%~63%.
From Fig. 6 and Fig. 7, Zn complex [Zn (HL) (HBPEP)] is maden, it is H to weigh feed molar proportioning4L︰
BPEP ︰ Zn (NO3)2︰ H2O ︰ CH3The ︰ 3658 of 18 ︰ of CN=30 ︰, 45 ︰ 8333 are more suitable, and the reaction time is 3-5 days more suitable：
The Zn complex [Zn (HL) (HBPEP)] of gainednPurer, fluorescence maximum emission wavelength (excites at 614nm in 550nm wavelength
Under), illustrate that this complex sends out stronger fluorescent red-orange, it is possible to as new fluorescent material.
Bibliography：
[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 (19)
1. fluorescent red-orange zinc coordination polymer [Zn (HL) (HBPEP)]n, monomer structure is as follows：
Wherein HL is
Organic carboxyl acid H4L sloughs the component after 3 carboxyl hydrogen atoms, H4L structural formula is
HBPEP is the component after containing n-donor ligand BPEP monoprotonated, and BPEP structural formula is
2. coordination polymer as claimed in claim 1, it is characterised in that：By zinc nitrate, part H4L and BPEP set out preparation and
Into the part H4L is a kind of multidentate ligand containing O, and the part BPEP is a kind of bidentate ligand containing stibazole,
Carboxyl O and pyridine N in part are coordinated the four-coordination metal-organic coordination polymer to be formed with central atom Zn.
3. the zinc coordination polymer of claim 1 or 2 [Zn (HL) (HBPEP)]nSynthetic method, it is characterised in that：Including such as
Lower step：Using solvent process for thermosynthesizing, raw material is weighed by following mol ratio：H4L ︰ BPEP ︰ Zn (NO3)2︰ H2O ︰ CH3CN=
The ︰ 380~3936 of 27~33 ︰, 16~20 ︰, 43~47 ︰ 7933~8733, raw material is mixed into 0.5~3h, in closed container
Reacted 3~5 days at 100~120 DEG C；After natural cooling, filtering, it is target product to obtain orange bulk crystals；Wherein,
H4L structural formula isBPEP structural formula is
4. method as claimed in claim 3, it is characterised in that：H4L ︰ BPEP ︰ Zn (NO3)2︰ H2O ︰ CH3CN mol ratio is 30 ︰
The ︰ 3658 of 18 ︰, 45 ︰ 8333.
5. the method as described in claim 3 or 4, it is characterised in that：Described closed container is reactor.
6. the method as described in claim 3 or 4, it is characterised in that：The described reaction time is 4 days.
7. method as claimed in claim 5, it is characterised in that：The described reaction time is 4 days.
8. the method as described in claim 3 or 4, it is characterised in that：Described reaction temperature is 110 DEG C.
9. method as claimed in claim 5, it is characterised in that：Described reaction temperature is 110 DEG C.
10. method as claimed in claim 6, it is characterised in that：Described reaction temperature is 110 DEG C.
11. method as claimed in claim 7, it is characterised in that：Described reaction temperature is 110 DEG C.
12. the method as described in claim 3 or 4, it is characterised in that：Described orange bulk crystals are washed with water, acetonitrile successively
Wash, spontaneously dry.
13. method as claimed in claim 5, it is characterised in that：Described orange bulk crystals are washed with water, acetonitrile successively,
Spontaneously dry.
14. method as claimed in claim 6, it is characterised in that：Described orange bulk crystals are washed with water, acetonitrile successively,
Spontaneously dry.
15. method as claimed in claim 7, it is characterised in that：Described orange bulk crystals are washed with water, acetonitrile successively,
Spontaneously dry.
16. method as claimed in claim 8, it is characterised in that：Described orange bulk crystals are washed with water, acetonitrile successively,
Spontaneously dry.
17. method as claimed in claim 9, it is characterised in that：Described orange bulk crystals are washed with water, acetonitrile successively,
Spontaneously dry.
18. method as claimed in claim 10, it is characterised in that：Described orange bulk crystals are washed with water, acetonitrile successively,
Spontaneously dry.
19. method as claimed in claim 11, it is characterised in that：Described orange bulk crystals are washed with water, acetonitrile successively,
Spontaneously dry.
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