CN103864825A - Mixed ligand-based zinc complex and preparation method thereof - Google Patents

Mixed ligand-based zinc complex and preparation method thereof Download PDF

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CN103864825A
CN103864825A CN201410036267.6A CN201410036267A CN103864825A CN 103864825 A CN103864825 A CN 103864825A CN 201410036267 A CN201410036267 A CN 201410036267A CN 103864825 A CN103864825 A CN 103864825A
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cyanopyridine
deionized water
sodium azide
ptz
dpa
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郭畅
黄安泉
官叶斌
朱昌海
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Anqing Normal University
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Anqing Normal University
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Abstract

The invention discloses a mixed ligand-based zinc (II) complex and a preparation method thereof. The method comprises the following step: preparing colorless lump crystal from zinc nitrate hexahydrate, sodium azide, 4-cyanopyridine and 2,2'-diphenyldicarboxylic acid in secondary deionized water by hydrothermal in situ reaction, wherein the molar ratio of zinc nitrate hexahydrate to sodium azide to 4-cyanopyridine to 2,2'-diphenyldicarboxylic acid is 2:2:2:1; the reaction medium is secondary deionized water; the specific steps are as follows: reacting at constant temperature of 180 DEG C for 3 days, then cooling to room temperature, filtering, washing and drying to obtain the colorless lump crystal; the chemical formula is Zn<2>(PTZ)<2>(DPA)(H<2>O)<2>; PTZ is 5-(4-pyridine) tetrazole monovalent anion obtained from sodium azide and 4-cyanopyridine by [2+3] in situ reaction under the hydrothermal condition; DPA is divalent anion of 2,2'-diphenyldicarboxylic acid. The complex belongs to a functional coordination complex, has a novel two-dimensional layer structure, is good in thermal stability, and can be further developed and applied as a molecular-based light-emitting material. The preparation method disclosed by the invention is simple and available in raw material.

Description

A kind of Zn complex based on mixed ligand and preparation method thereof
Technical field
The invention belongs to function ligand polymer and molecular based luminescent material technical field, particularly a kind of zinc (II) title complex that contains aromatic carboxylic acid and tetrazole mixed ligand and preparation method thereof.The title complex of inventing has novel two-dimensional layered structure, can be used as optical material by further Application and Development.
Background technology
A metal-organic complex is due to its abundant space topological structure, and in the potential application of the aspects such as separation, gas storage, selective catalysis and molecular recognition, and becomes an important research direction in crystal engineering field.According to the principle of crystal engineering, central metallic ions and the special organic ligand with particular geometric configuration can be realized rational design to a certain extent with synthetic.But owing to being subject to the impact of the factor such as coordination mode, coordination environment of organic ligand and metal ion, the target compound that appropriate design has a fixed structure is still a challenge concerning investigator.
Carboxylic acid is modal title complex bridge ligand, has multiple coordination mode with metal ion, easily produces the diversity of structure; And according to the degree of deprotonation, carboxylic acid itself can be simultaneously as hydrogen bond receptor with to body.The carboxylic-acid part that molecular structure is different, because the different coordination numbers of teeth, hapto spacing have very strong coordination ability and coordination mode flexibly.
And the title complex of tetrazole and derivative thereof has the effect of good optical, electrical, magnetic, storage hydrogen function and antimicrobial acivity, in coordination chemistry, medical chemistry, materials chemistry, is widely used.
Use Situ Hydrothermal self-assembling synthesizing method in the title complex of tetrazole is synthetic, can a step generation nitrine and cyanogen root [2+3] cycloaddition reaction, does not need prior synthetic ligands, has reduced middle-chain, environment-friendly high-efficiency.To tetrazole part, first synthetic reaction again obtains a lot of report of title complex at present, and the tetrazole title complex obtaining by reaction in－situ self-assembly often has charming structure and luminosity, expands space in addition at this area research.
This scheme of the invention relates to numerous ambits in theory as inorganic chemistry, organic chemistry, and polymer chemistry etc., the crystalline state luminescent material that obtains has potential using value, all have profound significance for basic and applied research.
Summary of the invention
The object of the present invention is to provide a kind of containing 5-(4-pyridine) tetrazole and 2,2 '-biphenyl dicarboxylic acid mixed ligand Zn (II) title complex with and preparation method thereof.Described title complex is first two-dimensional layer Zn (II) title complex that contains 5-(4-pyridine) tetrazole and 2,2`-biphenyl dicarboxylic acid mixed ligand.Its synthetic method is simple, productive rate is high, raw material is easy to get, and its crystalline material has good luminescent properties, can be used as potential luminescent material.
For achieving the above object, the invention provides following technology contents:
Chemical formula containing mixed ligand zinc (II) title complex provided by the invention is Zn 2(PTZ) 2(DPA) (H 2o) 2, wherein PTZ is 5-(4-pyridine) tetrazole univalent anion (warp [2+3] reaction in－situ under hydrothermal condition obtains for sodium azide and 4-cyanopyridine), DPA is the dianion of 2,2 '-biphenyl dicarboxylic acid.
The invention provides the preparation method containing mixed ligand zinc (II) title complex, it is characterized in that: by zinc nitrate hexahydrate, sodium azide, 4-cyanopyridine and 2,2 '-biphenyl dicarboxylic acid makes colourless bulk crystals through hydro-thermal reaction in－situ in secondary deionized water, wherein the mol ratio of zinc nitrate hexahydrate, sodium azide, 4-cyanopyridine and 2,2 '-biphenyl dicarboxylic acid is 2: 2: 2: 1.Reaction medium is secondary deionized water.Constant temperature 3 days at 180 ℃, then cool to room temperature, filters, and washing is dry, obtains colourless bulk crystals.
In the stainless steel cauldron that it is tetrafluoroethylene that described hydro-thermal reaction refers at liner, take secondary deionized water as reaction medium, utilize electric heating constant-temperature blowing drying box control temperature, make indissoluble or insoluble substance dissolves crystallization under normal conditions.
Under hydrothermal condition, there is the acquisition of [2+3] reaction in－situ through sodium azide and 4-cyanopyridine in described PTZ part.
Monocrystalline containing mixed ligand zinc (II) title complex provided by the invention, its constitutional features is: crystal belongs to oblique system, and spacer is C2/c, and unit cell parameters is: β=116.218 (2) °,
Figure BSA0000100783740000022
z=8.As shown in Figure 1, the asymmetric cell of this title complex is containing 2 independent center Zn (II) ion, 2 independent PTZ -part, a DPA 2-the H of part and 2 coordinations 2o molecule.Center Zn1 ion adopts octahedral coordination geometric configuration, and two axial coordination N atoms are respectively from the pyridine nitrogen atom of two different PTZ-parts, and the O atom on four equatorial planes comes from respectively a DPA 2-two H of part 2o molecule, wherein Zn1-O/N bond distance is
Figure BSA0000100783740000026
Figure BSA0000100783740000023
o/N-Zn1-O/N bond angle is 82.73 (10)～171.78 (12) ° of scopes.Center Zn2 ion adopts tetrahedral coordination geometric configuration, and two coordination N atoms are respectively from two different PTZ -the tetrazole nitrogen-atoms of part, two O atoms carry out respectively two DPA 2-part, wherein Zn2-O/N bond distance is
Figure BSA0000100783740000024
o/N-Zn2-O/N bond angle is 100.21 (11)～123.18 (12) ° of scopes.PTZ -part bridging Zn1 and Zn2 atom form regular one-dimensional chain along c-direction of principal axis, Zn1 in chain ... Zn2 distance is
Figure BSA0000100783740000025
dPA 2-the carboxyl of part is all with μ 2-bridging pattern connects Zn1 and Zn2 atom forms regular one-dimensional chain at b-direction of principal axis, Zn1 in chain ... Zn2 distance is
Figure BSA0000100783740000027
with the two dimensional surface stratiform structure that the one-dimensional chain of two types is intertwined to form, this two-dimensional layer is parallel to bc crystal face (shown in Fig. 2).Between contiguous two-dimensional layer, be piled into three-dimensional supramolecular structure (Fig. 3) by weak molecular interaction at a direction of principal axis.
Of the present invention containing the ultimate analysis of mixed ligand zinc (II) title complex: calculated value C 26h 20n 10o 6zn 2: C, 44.66; H, 2.88; N, 20.03. measured value: C, 44.59; H, 2.85; N, 20.19%.Instrument is VARIO EL III elemental analyser (Germany, Elementar).
Mixed ligand zinc (II) the title complex heat decomposition temperature that contains of the present invention, higher than 150 ℃ (Fig. 4), shows the thermodynamic stability that it has had.Instrument is STA-409PC Thermal Synthetic Analysis instrument (Germany, Netzsch).
Mixed ligand zinc (II) title complex that contains of the present invention at room temperature presents strong violet light character under the X-of 290nm optical excitation, and emission peak is positioned at 395nm place (Fig. 5), is expected to aspect luminescent material, have good application.Instrument is F-4500 (Japan, Hitachi).
Accompanying drawing explanation
The molecular structure of Fig. 1 mixed ligand zinc (II) title complex;
The two-dimensional layered structure figure of Fig. 2 mixed ligand zinc (II) title complex;
The structure cell accumulation graph of Fig. 3 mixed ligand zinc (II) title complex;
The thermogravimetric analysis curve of Fig. 4 mixed ligand zinc (II) title complex;
The room temperature solid fluorescence launching curve of Fig. 5 mixed ligand zinc (II) title complex.
Embodiment
The present invention is Zn containing the chemical formula of mixed ligand zinc (II) title complex 2(PTZ) 2(DPA) (H 2o) 2, wherein PTZ is 5-(4-pyridine) tetrazole univalent anion, DPA is the dianion of 2,2 '-biphenyl dicarboxylic acid.
Further set forth the present invention below in conjunction with concrete embodiment.
Embodiment: by Zn (NO 3) 2.6H 2o (59.2mg, 0.2mmol), 4-cyanopyridine (20.8mg, 0.2mmol), H 2dPA (24.2mg, O.1mmol) and NaN 3(13.2mg, 0.2mmol) adds in 12mL deionized water, in the stainless steel vessel of 25mL liner tetrafluoroethylene, seals, and is heated to 180 ℃ and keep 3 days, and then Slow cooling is to room temperature.Repeatedly clean with deionized water and anhydrous methanol, after air drying, just obtain colourless bulk crystals, based on Zn (NO 3) 2.6H 2o calculates productive rate and is about 72%.
Mixed ligand zinc (II) title complex that contains of the present invention further characterizes, and its process is as follows:
1, the described crystal structure determination containing mixed ligand zinc (II) title complex
Choose the monocrystalline of 0.22mm × 0.20mm × 0.19mm size, under 296.2K on Bruker Smart APEX II CCD single crystal diffractometer, with the Mo-k alpha-ray through graphite monochromatization for incident radiation,
Figure BSA0000100783740000032
scan mode is collected X-ray single crystal diffraction data, adopts method of least squares refine unit cell parameters, and SHELXL-97 direct method is resolved crystalline structure, and all non-hydrogen atoms carry out anisotropy refine by complete matrix method of least squares.H atom site theory mode calculative determination.The partial parameters of crystalline diffraction data gathering and structure refinement is in table 1, and crystalline structure as shown in Figures 1 to 3.
2, the described research of the thermal stability containing mixed ligand zinc (II) title complex
After washing, drying treatment, be heated to gradually 800 ℃ containing mixed ligand zinc (II) match crystal aspect product speed with 10 ℃/min under nitrogen protection from room temperature.As shown in Figure 4, this compound crystalline material thermogravimetric analysis curve table reveals three step Weight loses to thermogravimetric analysis curve.When the first step weightlessness occurs in 150 ℃, corresponding to losing two coordination H 2o molecule; When second step weightlessness occurs in 300 ℃, corresponding to losing a DPA 2-part; When the 3rd step weightlessness occurs in 320 ℃, corresponding to PTZ -part dissociation, until 800 ℃ of part PTZ -also there is no complete dissociation (shown in Fig. 4).
3, the described solid fluorescence performance study containing mixed ligand zinc (II) title complex
After washing, drying treatment, through fully grinding, under room temperature, carry out solid luminescence test containing mixed ligand zinc (II) match crystal aspect product.Under the X-of 290nm optical excitation, present strong violet light character, emission peak is positioned at 395nm place (shown in Fig. 5).Illustrate that it has by the value of further Application and Development aspect luminescent material.
The main crystallographic data of table 1 title complex and refine parameter
Figure BSA0000100783740000041
。

Claims (4)

1. the zinc based on mixed ligand (II) title complex, is characterized in that: described coordination chemistry formula Zn 2(PTZ) 2(DPA) (H 2o) 2, wherein PTZ is 5-(4-pyridine) tetrazole univalent anion (warp [2+3] reaction in－situ under hydrothermal condition obtains for sodium azide and 4-cyanopyridine), DPA is the dianion of 2,2 '-biphenyl dicarboxylic acid.
2. a complex preparation method as claimed in claim 1, it is characterized in that: by zinc nitrate hexahydrate, sodium azide, 4-cyanopyridine and 2,2 '-biphenyl dicarboxylic acid makes colourless bulk crystals through hydro-thermal reaction in－situ in secondary deionized water, wherein the mol ratio of zinc nitrate hexahydrate, sodium azide, 4-cyanopyridine and 2,2 '-biphenyl dicarboxylic acid is 2: 2: 2: 1.Reaction medium is secondary deionized water.Constant temperature 3 days at 180 ℃, then Slow cooling, to room temperature, filters, and washing, at air drying, obtains colourless bulk crystals fast.
3. complex preparation method as claimed in claim 2, it is characterized in that: in the stainless steel cauldron that it is tetrafluoroethylene that described hydro-thermal reaction refers at liner take secondary deionized water as reaction medium, utilize electric heating constant-temperature blowing drying box control temperature, make indissoluble or insoluble substance dissolves crystallization under normal conditions.
4. complex preparation method as claimed in claim 2, is characterized in that: described washings is secondary deionized water and anhydrous methanol.
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CN106700090A (en) * 2016-12-27 2017-05-24 吉林师范大学 Coordination polymer with triple interpenetration polycable structure, and preparation method thereof
CN107652439A (en) * 2017-09-22 2018-02-02 宁波大学 A kind of cadmium metal organic framework materials and its preparation method and application
CN109265473A (en) * 2018-11-28 2019-01-25 安庆师范大学 One kind zinc containing mixed ligand (II) metal organic complex and its preparation method and application

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106700090A (en) * 2016-12-27 2017-05-24 吉林师范大学 Coordination polymer with triple interpenetration polycable structure, and preparation method thereof
CN107652439A (en) * 2017-09-22 2018-02-02 宁波大学 A kind of cadmium metal organic framework materials and its preparation method and application
CN107652439B (en) * 2017-09-22 2020-07-03 宁波大学 Cadmium metal organic framework material and preparation method and application thereof
CN109265473A (en) * 2018-11-28 2019-01-25 安庆师范大学 One kind zinc containing mixed ligand (II) metal organic complex and its preparation method and application

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Application publication date: 20140618