CN107286201A - Stable chain Ni (II) complexes of amino acid with fluorescence property and preparation method thereof - Google Patents
Stable chain Ni (II) complexes of amino acid with fluorescence property and preparation method thereof Download PDFInfo
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- CN107286201A CN107286201A CN201710669681.4A CN201710669681A CN107286201A CN 107286201 A CN107286201 A CN 107286201A CN 201710669681 A CN201710669681 A CN 201710669681A CN 107286201 A CN107286201 A CN 107286201A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni
Abstract
The present invention relates to heat endurance Ni (II) complex with fluorescence property and preparation method thereof, it is related to transition-metal coordination technical field of polymer.Coordination chemistry formula is：{[Ni(L1)(H2O)3](CH3COO) }, wherein L1 is N (4 picolyl) (L) valine formic acid anion ligand.The preparation technology of the complex is using nickel acetate and N (4 picolyl) (L) valine sodium formate as reaction raw materials, and reaction obtains crystalline material under the conditions of low-temperature solvent heat.Synthetic method mild condition of the present invention, yield are high, easy to operate, favorable reproducibility.Complex crystal sample has preferable fluorescent effect, and thermal analysis is very well, has preferable application prospect in terms of fluorescent material.
Description
Technical field
The invention belongs to chemical science and technical field, more particularly to transition-metal coordination technical field of polymer, specifically
Ground, which is said, is related to N- (4- picolyls)-(L) valine nickel formate (II) complex and preparation method thereof, the nickel complex crystal
Sample is to have very strong fluorescent effect at 337nm in launch wavelength, and this complex has higher heat endurance, is expected in crystalline substance
Further applied in state fluorescent material field.
Background technology
Self-assembling technique is widely used in novel metal of the synthesis with stable micropore or meso-hole structure-organic in recent years
Framework material, this polyporous materials are shown in fields such as light, electricity, magnetic, catalysis, adsorbing separation, ion exchange, gas storages
Potential broad prospect of application (J.J.Bodwin, A.D.Cutland, R.G.Malkani, V.L.Pecoraro,
Coord.Chem.Rev. 2001,216-217,489-512.D.J.Tranchemontagne, J.L.Mendoza-Cort é s,
M.O ' Keeffe, O.M.Yaghi, Chem.Soc.Rev.2009,38,1257-1283.G.F é rey, C.Serre,
Chem.Soc.Rev.2009,38,1380-1399.).As the basic component units of protein, the side chain of natural amino acid has
Flexible coordination mode and good hydrogen bond assembling ability, can produce certain influence, therefore be to the 26S Proteasome Structure and Function of protein
It is potential construct functional complexes idealized unit cell (A.C. Kathalikkattil, K.K.Bisht, N.A.Alcalde,
E.Suresh, Cryst.Growth Des.2011,11,1631-1641.)；However, as part being difficult structure merely with amino acid
The complex supramolecular materials with specific physicochemical property are built out, by introducing the function with stronger coordination ability in aminoterminal
Group's such as pyridine groups, make it cooperate with assembling with the hydroxy-acid group of amino acid, can construct out stable multi-function metal-organic bone
Frame material (L.A.Meiske, R.A.Jacobson, R.J.Angelici, Inorg. Chem.1980,19,2028-2034；
X.Li, T.liu, B.Hu, G.Li, H.Zhang, R.Gao, Cryst.Growth Des.2010,10,3051-3059).N-(4-
Picolyl)-(L) amino acid once constructed as physiologically active part the metals such as cobalt, zinc complex (T.Kundu,
S.C.Sahoo, R.Banerjee, CrystEngComm.2013,15,9634-9640.T.Kundu, S.C. Sahoo,
S.Saha, R.Banerjee, Chem.Commun.2013,5262-5264), and there is not been reported for the complex of associated metal nickel；
In addition, the nickel complex with specific structure may also used as fluorescent material (Z.Lu, L.Wen, Z.Ni, Y.Li, H.Zhu,
Q.Meng, Cryst.Growth Des.2007,7,268-274).
In view of this, inventor spy proposes a kind of one-dimensional chain N- (4- picolyls)-(L) with fluorescent characteristic
Valine nickel formate (II) complex and its preparation technology, to fill up the blank of domestic and international association area.
The content of the invention
The purpose of the present invention be disclose a kind of N- (4- picolyls)-(L) valine nickel formate (II) complex and its
Preparation method, the complex can be as fluorescent material, and heat endurance is good and preparation method is simple and easy to apply, and yield is high, in material supply section
Field has potential application value.
The chemical formula of heat endurance chain nickel (II) complex with fluorescence property that the present invention is provided is： {[Ni
(L1)(H2O)3](CH3COO) }, wherein L1 is N- (4- picolyls)-(L) valine formic acid anion ligand, and its molecular formula is such as
Under：
The molecular formula of above-mentioned nickel (II) complex is：C13H24N2NiO7, molecular weight is：379.05.It is of the present invention to match somebody with somebody
Compound construction unit is as follows：The complex belongs to monoclinic system, and space group is P21, cell parameter is：A=6.0738 (18), b=
15.342 (4),α=90 °, β=94.899 (7) °, γ=90 °, its basic coordination structure is a monokaryon
Unit.
The complex of the nickel (II) has three-dimensional hydrogen bond network structure, wherein, each Ni (II) metal center is in octahedral
Body hexa-coordinate configuration, respectively with 2 L1 parts and 3 water molecule coordinations；Each L1 parts 2 Ni (II) ions of bridging, wherein
Amino acid moiety chelates Ni (II) ion with N, O bidentates, and pyridine nitrogen monodentate ligand connects another Ni (II) ion, is formed
One-dimensional catenary structure.
The preparation method of the complex of heat endurance nickel (II) with fluorescence property, is carried out as steps described below：
It is at 20 DEG C of room temperature, the nickel salt of metering and N- (4- picolyls)-(L) valine sodium formate is soluble in water in ethanol
With the in the mixed solvent of water, several minutes of ultrasonic vibration is after temperature is gradually raised to reaction temperature by room temperature in 360min in thermal response kettle
Degree, is incubated 5 days, then temperature is cooled to 20 DEG C of room temperature from temperature programming in 360min, is matched somebody with somebody at the reaction temperatures
The green particles shape crystal of compound, it is collected by filtration, then washed respectively with methanol, ether, is dried, you can obtain with glimmering
The complex of the heat endurance nickel (II) of optical property.
The volume ratio of wherein described second alcohol and water is 2: 1~1: 2.
The mol ratio of wherein described nickel salt and N- (4- picolyls)-(L) valine sodium formate is 1: 1~1: 1.5.
Wherein described nickel salt is the metallic nickels such as nickel acetate, nickel chloride, nickel sulfate, hydrochloric acid nickel, nickel nitrate or nickelous perchlorate
Salt.
Wherein described range of reaction temperature is 90 DEG C~170 DEG C.
The present invention is using solvent thermal reaction method and a kind of into nickel for containing N- (4- picolyls)-(L) valine formic acid
(II) complex, required consersion unit is simple, and operation is simple, and reproducibility is good, and the complex prepared has heat
Stability is good, the advantages of yield is high, is expected to be used widely in fluorescent crystal Material Field.
Brief description of the drawings
Fig. 1 is the coordination environment containing Ni (II) in N- (4- picolyls)-(L) valine nickel formate (II) complex
Figure；
Fig. 2 is containing N- (4- picolyls)-chain of (L) valine nickel formate (II) complex along crystallography c directions
Structure chart；
Fig. 3 is containing the three-dimensional hydrogen bond network structure of N- (4- picolyls)-(L) valine nickel formate (II) complex；
Fig. 4 is the Solid fluorescene spectrum figure containing N- (4- picolyls)-(L) valine nickel formate (II) complex；
Fig. 5 is the thermal gravimetric analysis curve figure containing N- (4- picolyls)-(L) valine nickel formate (II) complex.
Embodiment
The preparation of the complex of experimental example 1：
0.2mmol N- (4- picolyls)-(L) valine sodium formate (55mg), 0.2mmol nickel acetates (50mg) mixing
In 7 mL second alcohol and waters (volume ratio is 2: 1), wherein described nickel salt and N- (4- picolyls)-(L) valine sodium formate
Mol ratio is 1: 1.Mixture ultrasonic vibration 5 minutes is after temperature is gradually raised to 90 by room temperature in 360min in hydrothermal reaction kettle
DEG C, 90 DEG C are incubated 5 days, and then temperature is gradually dropped to 20 DEG C from 90 DEG C in 360min, and last room temperature is filtrated to get green particles
Shape monocrystalline, is then washed with 10mL methanol and 10mL ether respectively, is spontaneously dried.Yield is 75% (being based on L1, similarly hereinafter).
The preparation of the complex of experimental example 2：
0.2mmol N- (4- picolyls)-(L) valine sodium formate (55mg), 0.3mmol nickel acetates (75mg) mixing
In 7 mL second alcohol and waters (volume ratio is 2: 1), wherein described nickel salt and N- (4- picolyls)-(L) valine sodium formate
Mol ratio is 1: 1.5.Mixture ultrasonic vibration 5 minutes is after temperature is gradually raised to 90 by room temperature in 360min in hydrothermal reaction kettle
DEG C, 90 DEG C are incubated 3 days, and then temperature is gradually dropped to 20 DEG C from 90 DEG C in 360min, and last room temperature is filtrated to get green particles
Shape monocrystalline, is then washed with 10mL methanol and 10mL ether respectively, is spontaneously dried.Yield is 69%.
The preparation of the complex of experimental example 3：
0.2mmol N- (4- picolyls)-(L) valine sodium formate (55mg), 0.2mmol nickel acetates (50mg) mixing
In 7 mL second alcohol and waters (volume ratio is 1: 2), wherein described nickel salt and N- (4- picolyls)-(L) valine sodium formate
Mol ratio is 1: 1.Mixture ultrasonic vibration 5 minutes is after temperature is gradually raised to 90 by room temperature in 360min in hydrothermal reaction kettle
DEG C, 90 DEG C are incubated 3 days, and then temperature is gradually dropped to 20 DEG C from 90 DEG C in 360min, and last room temperature is filtrated to get green particles
Shape monocrystalline, is then washed with 10mL methanol and 10mL ether respectively, is spontaneously dried.Yield is 71%.
The preparation of the complex of experimental example 4：
0.2mmol N- (4- picolyls)-(L) valine sodium formate (55mg), 0.2mmol nickel acetates (50mg) mixing
In 7 mL second alcohol and waters (volume ratio is 2: 1), wherein described nickel salt and N- (4- picolyls)-(L) valine sodium formate
Mol ratio is 1: 1.Mixture ultrasonic vibration 5 minutes is after temperature is gradually raised to 170 by room temperature in 360min in hydrothermal reaction kettle
DEG C, 170 DEG C are incubated 3 days, and then temperature is gradually dropped to 20 DEG C from 170 DEG C in 360min, and last room temperature is filtrated to get green
Granular single crystal, is then washed with 10mL methanol and 10mL ether respectively, is spontaneously dried.Yield is 67%.
The preparation of the complex of experimental example 5：
0.3mmol N- (4- picolyls)-(L) valine sodium formate (83mg), 0.2mmol nickel acetates (50mg) mixing
In 7 mL second alcohol and waters (volume ratio is 2: 1), wherein described nickel salt and N- (4- picolyls)-(L) valine sodium formate
Mol ratio is 1: 1.5.Mixture ultrasonic vibration 5 minutes is after temperature is gradually raised to by room temperature in 360min in hydrothermal reaction kettle
100 DEG C, kept for 100 DEG C 3 days, then temperature is gradually dropped to 20 DEG C from 100 DEG C in 360min, and last room temperature is filtrated to get green
Graininess monocrystalline, is then washed with 10mL methanol and 10mL ether respectively, is spontaneously dried.Yield is 67%.
The preparation of the complex of experimental example 6：
0.2mmol N- (4- picolyls)-(L) valine sodium formate (55mg), 0.2mmol nickel nitrates (58mg) and 7mL
The mixture of second alcohol and water (volume ratio is 1: 2), wherein described nickel salt and N- (4- picolyls)-(L) valine sodium formate
Mol ratio be 1: 1.Mixture ultrasonic vibration 5 minutes is after temperature is gradually raised to by room temperature in 360min in hydrothermal reaction kettle
170 DEG C, 170 DEG C are incubated 3 days, and then temperature is gradually dropped to 20 DEG C from 170 DEG C in 360min, and last room temperature is filtrated to get green
Graininess monocrystalline, is then washed with 10mL methanol and 10mL ether respectively, is spontaneously dried.Yield is 62%.
The sign of the complex of experimental example 7：
(1) structure determination of complex
Crystal structure determination uses Bruker Apex II CCD diffractometers, under 296 (2) K, with through graphite monochromatised
Mo K alpha raysPoint diffraction is collected with ω scan modes, the data of collection are used in combination by SAINT programe reductions
SADABS methods carry out semiempirical absorption correction.Structure elucidation and refine be respectively adopted SHELXTL programs SHELXS and
SHELXL is completed, by complete matrix least square method to F2It is modified the coordinate that obtains whole non-hydrogen atoms and each to different
Property parameter.All hydrogen atoms are fixed on parent during structure refinement by theory, are assigned than parent displacement parameter slightly
The isotropism displacement parameter of (C-H, 1.2 or O/N-H, 1.5 times) greatly.Detailed axonometry data are shown in Table 1.Structure is shown in figure
1st, 2 and 3.Fig. 1：The coordination context diagram of nickel complex；Fig. 2：Complex one-dimensional catenary structure schematic diagram；Fig. 3：Complex three-dimensional hydrogen
Key network structure.
(2) the solid fluorescence performance study of complex
Complex crystal sample after enrichment processing, by further milled processed, carries out the test of solid fluorescence：Coordinate
Thing is excited at 337nm, and the emission peak of maximum is obtained at 433nm, Fig. 4 (INSTRUMENT MODELs are seen：Varian Cary Eclipse
spectrometer)。
(3) heat endurance of complex is characterized
The thermogravimetric analysis of complex shows that its main body framework is appointed at 280 DEG C or so and can be so stabilized, with higher heat
Stability, provides heat endurance as the further development and application of crystalline material for it and ensures, see Fig. 5 (INSTRUMENT MODELs：TG/
DTA-6300)。
Above example is merely to illustrate present disclosure, in addition, and the present invention also has other embodiment.But it is all
The technical scheme formed using equivalent substitution or equivalent deformation mode is all fallen within protection scope of the present invention.
{ [Ni (the L1) (H of table 12O)3](CH3COO crystallographic parameter) }
aR=∑s | | Fo|-|Fc||/∑|Fo|.
bRw=[∑ [w (Fo 2-Fc 2)2]/∑w(Fo 2)2]1/2.
cGOF={ ∑ [w (Fo 2-Fc 2)2]/(n-p)}1/2。
Claims (6)
1. heat endurance chain nickel (II) complex with fluorescence property, it is characterised in that its chemical formula is：{[Ni(L1)
(H2O)3](CH3COO) }, wherein L1 is N- (4- picolyls)-(L) valine formic acid anion ligand, and its molecular formula is as follows：
2. the preparation method of the complex of the heat endurance nickel (II) with fluorescence property described in claim 1, its feature exists
In carrying out as steps described below：
At room temperature, the nickel salt of metering and N- (4- picolyls)-(L) valine sodium formate are dissolved in the mixed solvent of second alcohol and water
In in hydrothermal reaction kettle ultrasonic vibration reaction temperature is gradually raised to by room temperature after temperature in 360min within 5 minutes, reaction temperature
The lower insulation of degree 3 days, then temperature is cooled to 20 DEG C of room temperature from temperature programming in 360min, obtains the purple of complex
Bulk crystalline, it is collected by filtration, and is then washed respectively with methanol, ether, is dried, you can obtain the heat with fluorescence property steady
The complex of qualitative nickel (II), yield is higher (＞ 60%).
3. the preparation method of the complex of the heat endurance nickel (II) according to claim 2 with fluorescence property, it is special
Levy and be that the volume ratio of wherein described second alcohol and water is 2: 1~1: 2.
4. the preparation method of the complex of the heat endurance nickel (II) according to claim 2 with fluorescence property, it is special
Levy and be that the mol ratio of wherein described nickel salt and N- (4- picolyls)-(L) valine sodium formate is 1: 1~1: 1.5.
5. the preparation method of the complex of the heat endurance nickel (II) according to claim 2 with fluorescence property, it is special
Levy and be that wherein described nickel salt is nickel acetate, nickel chloride, nickel sulfate, hydrochloric acid nickel, nickel nitrate or nickelous perchlorate.
6. the preparation method of the complex of the heat endurance nickel (II) according to claim 2 with fluorescence property, it is special
Levy and be that wherein described range of reaction temperature is 90 DEG C~170 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108384017A (en) * | 2017-12-29 | 2018-08-10 | 济南大学 | A kind of chirality Ni（II）Amino Schiff base coordination polymer and preparation method thereof |
| CN108821350A (en) * | 2018-05-29 | 2018-11-16 | 昆明理工大学 | A kind of preparation method of transition metal salt amine complex |
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| CN103113415A (en) * | 2012-09-20 | 2013-05-22 | 常州大学 | Thermally stable Ni coordination compound with fluorescence property and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108384017A (en) * | 2017-12-29 | 2018-08-10 | 济南大学 | A kind of chirality Ni（II）Amino Schiff base coordination polymer and preparation method thereof |
| CN108384017B (en) * | 2017-12-29 | 2020-11-03 | 济南大学 | Chiral Ni (II) amino acid Schiff base coordination polymer and preparation method thereof |
| CN108821350A (en) * | 2018-05-29 | 2018-11-16 | 昆明理工大学 | A kind of preparation method of transition metal salt amine complex |
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