CN102993220B - 5-bromoisophthalic acid zinc complex and preparation method thereof - Google Patents
5-bromoisophthalic acid zinc complex and preparation method thereof Download PDFInfo
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- CN102993220B CN102993220B CN201210517945.1A CN201210517945A CN102993220B CN 102993220 B CN102993220 B CN 102993220B CN 201210517945 A CN201210517945 A CN 201210517945A CN 102993220 B CN102993220 B CN 102993220B
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Abstract
The invention relates to a 5-bromoisophthalic acid zinc complex and a preparation method thereof. The chemical formula of the complex is shown in the specification, wherein L is a 5-bromoisophthalic acid anionic ligand, and dpds is 4, 4'-bis(4-pyridyl) disulfide. The preparation method comprises the following steps: dissolving 5-bromoisophthalic acid, alkali, dpds and a metal zinc salt in water under hydrothermal conditions, sealing in a reaction kettle, heating to a certain temperature at the rate of 10 DEG C/hour, maintaining the temperature for 3 days, and then naturally cooling to room temperature to get a product disclosed by the invention. The complex has the advantages of good stability, simplicity in synthesis, convenience in operation, high yield, good reproducibility and the like, and an obtained crystalline material is expected to get further research and development applications in the field of fluorescent materials.
Description
Technical field
The present invention relates to d
10metal complex fluorescent Material Field, is specifically related to a kind of 5-bromine m-phthalic acid Zn complex and preparation method.
Background technology
At present, by organic ligand and metallic ion coordination self-assembly or controlled self-assembly and the research of the various metal-organic coordination polymer materials that form is very active, this is because ligand polymer not only has interesting and various molecular structure and topological framework, the more important thing is that it shows tempting application prospect in field of new such as fluorescence, absorption, catalysis, magnetic.M-phthalic acid and derivative thereof are the important bridge ligands of a class, react and construct some molecular based coordination polymer materials that obtain by extensive synthetic report, and show good Potential performance with this class part with metal ion.
Summary of the invention
The advantages such as the object of the invention is to open a kind of 5-bromine m-phthalic acid Zn complex and preparation method thereof, its synthetic method is simple, easy to operate, and has good stability, and productive rate height and reproducibility are good.
For achieving the above object, the technical scheme adopting is in the present invention: a kind of 5-bromine m-phthalic acid Zn complex, and chemical formula is:
, n is greater than 1;
Described 5-bromine m-phthalic acid Zn complex crystal belongs to rhombic system, and spacer is
pbca, unit cell parameters is
a=20.435 (2)
,
b=17.3253 (17)
,
c=21.628 (2)
,
α=90 °,
β=90 °,
γ=90 °,
v=7657.3 (13)
;
Described title complex basic structure is an interspersed network structure of three-dimensional quadruple with lfm topology, and basic structural unit exists two kinds of different Zn
iIcoordination environment, Zn1 and Zn2 are tetrahedral coordination, respectively with two Sauerstoffatoms of two 5-bromine m-phthalic acids and two 4, two nitrogen-atoms coordinations of 4 '-bis-pyridine disulfides; Zn
iIbe the three-dimensional structure with lfm topology in spatial spread by the bridge linking effect of part.Such three-dimensional structure and other three structures are mutually interted and are formed three-dimensional quadruple and intert network.
Wherein L is 5-bromine m-phthalic acid anion ligand, and skeleton symbol is as follows:
；
Wherein dpds is 4,4 '-bis-pyridine disulfides, and skeleton symbol is as follows:
。
The preparation method of 5-bromine m-phthalic acid Zn complex: under the condition of hydro-thermal, by 5-bromine m-phthalic acid, mineral alkali, 4,4 '-bis-pyridine disulfides and metal zinc salt are soluble in water, and enclose in reactor, be heated to 120 ~ 160 DEG C with the speed of 10 DEG C per hour, maintain 3 days, then natural condition drop to room temperature, can obtain colourless bulk crystals, the colourless bulk crystals of collecting, successively through washing, drying treatment, is obtained to target product.
Every 1L water adds the 5-bromine m-phthalic acid of 0.005 ~ 0.015 mol, 4,4 '-bis-pyridine disulfides, the zinc salt of 0.005 ~ 0.015 mol and the mineral alkali of 0.005 ~ 0.015 mol of 0.005 ~ 0.015 mol.
Described zinc salt is zinc acetate or zinc perchlorate.
Described mineral alkali is potassium hydroxide or sodium hydroxide, and the effect of alkali is to adjust pH value, and conventional mineral alkali all can be realized time object, and adding of organic bases may be served as template, can not generate this product.
beneficial effect
The advantages such as the title complex that synthetic method provided by the invention obtains, has good stability, synthetic simple, easy to operate, and productive rate height and reproducibility are good.The fluorescence data of crystal prototype shows that this type of title complex has stable fluorescence property, can be used as fluorescent material and is applied at material science.The thermogravimetric analysis of title complex characterizes and shows that its skeleton still can stable existence 290 DEG C of left and right, has certain thermostability, for its further Application and Development as material provides guarantee.
Brief description of the drawings
The coordination environment figure of zinc in 5-bromine m-phthalic acid Zn complex prepared by Fig. 1 embodiment 1;
The three-dimensional network figure of 5-bromine m-phthalic acid Zn complex prepared by Fig. 2 embodiment 1;
The topological network of 5-bromine m-phthalic acid Zn complex prepared by Fig. 3 embodiment 1;
The infared spectrum of 5-bromine m-phthalic acid Zn complex prepared by Fig. 4 embodiment 1;
Powdery diffractometry (PXRD) figure of 5-bromine m-phthalic acid Zn complex prepared by Fig. 5 embodiment 1;
5-bromine m-phthalic acid Zn complex thermogravimetric curve figure prepared by Fig. 6 embodiment 1;
The solid state fluorescence spectrogram of 5-bromine m-phthalic acid Zn complex prepared by Fig. 7 embodiment 1.
Embodiment
5-bromine m-phthalic acid Zn complex of the present invention, chemical formula is:
, n is greater than 1, and complex crystal belongs to rhombic system, and spacer is
pbca, unit cell parameters is
a=20.435 (2)
,
b=17.3253 (17)
,
c=21.628 (2)
,
α=90 °,
β=90 °,
γ=90 °,
v=7657.3 (13)
.Basic structure is an interspersed network structure of three-dimensional quadruple with lfm topology, and basic structural unit exists two kinds of different Zn
iIcoordination environment, Zn1 and Zn2 are tetrahedral coordination, respectively with two nitrogen-atoms coordinations of two Sauerstoffatoms and two dpds of two 5-bromine m-phthalic acids; Zn
iIbe the three-dimensional structure with lfm topology in spatial spread by the bridge linking effect of part.Such three-dimensional structure and other three structures are mutually interted and are formed three-dimensional quadruple and intert network.
Wherein L is 5-bromine m-phthalic acid anion ligand, and skeleton symbol is as follows:
；
Wherein dpds is 4,4 '-bis-(4-pyridine) disulfide, and skeleton symbol is as follows:
。
embodiment mono-
By 5-bromine m-phthalic acid (0.1 mmol, 24.5 mg), potassium hydroxide (0.1 mmol, 5.6 mg), dpds (22.4 mg, 0.1 mmol) and zinc acetate (24.0 mg, 0.1mmol) in water-soluble (12 mL), enclose in the reactor of 25 mL, be heated to 120 DEG C with the speed of 10 DEG C per hour, maintain this temperature 3 days, be then naturally cooled to room temperature, can obtain colourless bulk crystals, by this crystal separation out, through washing, drying treatment, obtain target product, productive rate approximately 50% successively.Main infrared absorption peak is: 3048 w, 1588 s, 1557 s, 1482 m, 1419 s, 1334 s, 1220 m, 1095 m, 1063 m, 1021 m, 812 s, 767 s, 714 s.
Getting the 5-bromine m-phthalic acid Zn complex that embodiment mono-makes further characterizes as follows:
(1) crystal structure determination of title complex
The monocrystalline of choosing suitable size at room temperature carries out X-ray diffraction experiment.Collect diffraction data at Bruker Apex II X-ray single crystal diffractometer, with the Mo of graphite monochromator monochromatization
k αray (
λ=0.71073
), Yi φ – ω mode is collected diffraction data.All data warp
lpthe factor and experience absorption correction, crystalline structure adopts SHELXS-97 program to be solved by direct method, and hydrogen atom is synthesized by difference fourier and is fixed on calculated optimum position to be determined.Use SHELX-97 programs, to whole non-hydrogen atoms and anisotropy thermal parameter thereof carried out based on
f 2complete matrix least-squares refinement.Detailed axonometry data are in table 1; Important bond distance and bond angle data are in table 2.Crystalline structure is shown in Fig. 1 and Fig. 2, and Fig. 3 is shown in by the topological network of title complex.
The main crystallographic data of table 1 title complex
The important bond distance of table 2 (
) and bond angle (°)
Symmetrical code: #1:x-1/2, y ,-z+3/2; #2:-x+1, y+1/2 ,-z+5/2.
(2) Infrared Characterization of title complex
The infared spectrum of title complex is shown in Fig. 4.(instrument model: NICOLET 6700 Fourier infrared spectrographs).
(3) the PXRD phase purity of title complex characterizes
The PXRD of title complex characterizes and shows that it has reliable phase purity, for its application as fluorescent material provides guarantee, sees Fig. 5.(instrument model: Bruker/D8 Advance).
(4) thermostability of title complex characterizes
The thermogravimetric analysis of title complex characterizes and shows that its skeleton still can stable existence 290 DEG C of left and right, has certain thermostability, for its further Application and Development as material provides thermostability guarantee, sees Fig. 6.(instrument model: SII EXStar6000 TG/DTA6300).
(5) the solid fluorescence performance study of title complex
Enrichment complex crystal sample after treatment carries out the test of solid fluorescence: title complex excites at 326 nm places, obtains an emission peak at 401 nm places, sees Fig. 7.(instrument model: HITACHI/F-4500).
Can be seen by above-mentioned characterization result, complex crystal of the present invention is characterized in that described complex crystal belongs to rhombic system, and spacer is
pbca, unit cell parameters is
a=20.435 (2)
,
b=17.3253 (17)
,
c=21.628 (2)
,
α=90 °,
β=90 °,
γ=90 °,
v=7657.3 (13)
.Basic structure is an interspersed network structure of three-dimensional quadruple with lfm topology, and basic structural unit exists two kinds of different Zn
iIcoordination environment, Zn1 and Zn2 are tetrahedral coordination, respectively with two nitrogen-atoms coordinations of two Sauerstoffatoms and two dpds of two 5-bromine m-phthalic acids; Zn
iIbe the three-dimensional structure with lfm topology in spatial spread by the bridge linking effect of part.Such three-dimensional structure and other three structures are mutually interted and are formed three-dimensional quadruple and intert network.
embodiment bis-
By 5-bromine m-phthalic acid (0.06 mmol, 14.7 mg), potassium hydroxide (0.18 mmol, 10.08 mg), dpds (13.44 mg, 0.06 mmol) and zinc acetate (43.2 mg, 0.18 mmol) in water-soluble (12 mL), enclose in the reactor of 25mL, be heated to 130 DEG C with the speed of 10 DEG C per hour, maintain this temperature 3 days, be then naturally cooled to room temperature, can obtain colourless bulk crystals, by this crystal separation out, through washing, drying treatment, obtain target product, productive rate approximately 52% successively.
embodiment tri-
By 5-bromine m-phthalic acid (0.18mmol, 44.1 mg), sodium hydroxide (0.06 mmol, 3.36 mg), dpds (40.32 mg, 0.18 mmol) and zinc acetate (14.4 mg, 0.06 mmol) in water-soluble (12 mL), enclose in the reactor of 25mL, be heated to 130 DEG C with the speed of 10 DEG C per hour, maintain this temperature 3 days, be then naturally cooled to room temperature, can obtain colourless bulk crystals, by this crystal separation out, through washing, drying treatment, obtain target product, productive rate approximately 45% successively.
embodiment tetra-
By 5-bromine m-phthalic acid (0.12 mmol, 29.4 mg), sodium hydroxide (0.12 mmol, 6.72 mg), dpds (26.88 mg, 0.12 mmol) and zinc acetate (28.8 mg, 0.12 mmol) in water-soluble (12 mL), enclose in the reactor of 25mL, be heated to 160 DEG C with the speed of 10 DEG C per hour, maintain this temperature 3 days, be then naturally cooled to room temperature, can obtain colourless bulk crystals, by this crystal separation out, through washing, drying treatment, obtain target product, productive rate approximately 47% successively.
Above embodiment is only for illustrating content of the present invention, and in addition, the present invention also has other embodiment.But all employings are equal to replaces or the technical scheme that forms of equivalent deformation mode all drops in protection scope of the present invention.
Claims (2)
1. a 5-bromine m-phthalic acid Zn complex, is characterized in that: the chemical formula of described 5-bromine m-phthalic acid Zn complex is:
, described 5-bromine m-phthalic acid Zn complex crystal belongs to rhombic system, and spacer is
pbca, unit cell parameters is
a=20.435 (2),
b=17.3253 (17),
c=21.628 (2),
α=90 °,
β=90 °,
γ=90 °,
v=7657.3 (13)
3;
Wherein L is 5-bromine m-phthalic acid anion ligand, and skeleton symbol is as follows:
；
Wherein dpds is 4,4 '-bis-(4-pyridine) disulfide, and skeleton symbol is as follows:
。
2. the preparation method of 5-bromine m-phthalic acid Zn complex as claimed in claim 1, it is characterized in that: under the condition of hydro-thermal, by soluble in water to 5-bromine m-phthalic acid, mineral alkali, dpds and zinc salt, and enclose in reactor, be heated to 120 ~ 160 DEG C with the temperature rise rate of 10 DEG C per hour, be incubated afterwards 3 days, then natural condition drop to room temperature, can obtain colourless bulk crystals, the colourless bulk crystals of collecting, successively through washing, drying treatment, is obtained to target product;
Every 1 L water adds the 5-bromine m-phthalic acid of 0.005 ~ 0.015 mol, the zinc salt of dpds, 0.005 ~ 0.015 mol and the mineral alkali of 0.005 ~ 0.015 mol of 0.005 ~ 0.015 mol;
Described zinc salt is zinc acetate, and described mineral alkali is potassium hydroxide or sodium hydroxide.
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| CN104086575B (en) * | 2014-06-25 | 2016-03-30 | 河南工程学院 | Two (pyridine)-(4-HBA)-chloro-zinc (II) title complex and preparation method thereof |
| CN105001247B (en) * | 2015-07-15 | 2018-03-09 | 洛阳师范学院 | 4 bromine M-phthalic acids and 1,4 2 (methylene of imidazoles 1) benzene mixture cadmium complexes and preparation method |
| CN105801607B (en) * | 2016-04-19 | 2018-05-22 | 广东共力建材有限公司 | A kind of PVC heat stabilizer and preparation method thereof |
| CN106380606A (en) * | 2016-09-12 | 2017-02-08 | 桂林理工大学 | Zinc isophthalate coordination polymer and preparation method thereof |
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| CN101993421B (en) * | 2009-08-25 | 2014-04-16 | 中国科学院福建物质结构研究所 | Synthesis and application of blue-fluorescence luminous zinc metal complex |
| CN101993690A (en) * | 2009-08-25 | 2011-03-30 | 中国科学院福建物质结构研究所 | IIB metal organic complex fluorescent light-emitting material |
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