CN102993220A - 5-bromoisophthalic acid zinc complex and preparation method thereof - Google Patents

5-bromoisophthalic acid zinc complex and preparation method thereof Download PDF

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CN102993220A
CN102993220A CN2012105179451A CN201210517945A CN102993220A CN 102993220 A CN102993220 A CN 102993220A CN 2012105179451 A CN2012105179451 A CN 2012105179451A CN 201210517945 A CN201210517945 A CN 201210517945A CN 102993220 A CN102993220 A CN 102993220A
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bromine
complex
phthalic acid
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dpds
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CN102993220B (en
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马录芳
韩民乐
王建革
张永花
尹卫东
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Luoyang Normal University
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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

5-bromine m-phthalic acid Zn complex and preparation method thereof
Technical field
The present invention relates to d 10The metal 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, construct some molecular based coordination polymer materials that obtain with this class part and metal ion reaction and are extensively synthesized report, and show good Potential performance.
Summary of the invention
The advantages such as the object of the invention is to disclose a kind of 5-bromine m-phthalic acid Zn complex and preparation method thereof, its synthetic method is simple, and is easy to operate, and has good stability, and productive rate height and reproducibility are good.
The present invention for achieving the above object, the technical scheme that adopts is: a kind of 5-bromine m-phthalic acid Zn complex, chemical formula is:
Figure 673673DEST_PATH_IMAGE001
, 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)
Figure 49290DEST_PATH_IMAGE002
, b=17.3253 (17)
Figure 404661DEST_PATH_IMAGE002
, c=21.628 (2)
Figure 877231DEST_PATH_IMAGE002
, α=90 °, β=90 °, γ=90 °, V=7657.3 (13)
Figure 662784DEST_PATH_IMAGE003
Described title complex basic structure is an interspersed network structure of three-dimensional quadruple with lfm topology, and there are two kinds of different Zn in basic structural unit 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 '-two pyridine disulfides; Zn IIBridge linking effect by part is the three-dimensional structure with lfm topology in spatial spread.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:
Figure 588015DEST_PATH_IMAGE004
；
Wherein dpds is 4,4 '-two pyridine disulfides, and skeleton symbol is as follows:
Figure 750006DEST_PATH_IMAGE005
。
The preparation method of 5-bromine m-phthalic acid Zn complex: under the condition of hydro-thermal, with 5-bromine m-phthalic acid, mineral alkali, 4,4 '-two pyridine disulfides and metal zinc salt are soluble in water, and in the inclosure reactor, be heated to 120 ~ 160 ℃ with 10 ℃ speed per hour, kept 3 days, then natural condition drop to room temperature, can obtain colourless bulk crystals, the successively process washing of colourless bulk crystals, drying treatment with collecting obtain target product.
Every 1L water adds 5-bromine m-phthalic acid, 4,4 '-two pyridine disulfides of 0.005 ~ 0.015 mol, 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 the pH value, and mineral alkali commonly used all can be realized time purpose, and the adding of organic bases may 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, and is 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 about 290 ℃, has certain thermostability, for its further Application and Development as material provides assurance.
Description of drawings
The coordination environment figure of zinc in the 5-bromine m-phthalic acid Zn complex of Fig. 1 embodiment 1 preparation;
The three-dimensional network figure of the 5-bromine m-phthalic acid Zn complex of Fig. 2 embodiment 1 preparation;
The topological network of the 5-bromine m-phthalic acid Zn complex of Fig. 3 embodiment 1 preparation;
The infared spectrum of the 5-bromine m-phthalic acid Zn complex of Fig. 4 embodiment 1 preparation;
Powdery diffractometry (PXRD) figure of the 5-bromine m-phthalic acid Zn complex of Fig. 5 embodiment 1 preparation;
The 5-bromine m-phthalic acid Zn complex thermogravimetric curve figure of Fig. 6 embodiment 1 preparation;
The solid state fluorescence spectrogram of the 5-bromine m-phthalic acid Zn complex of Fig. 7 embodiment 1 preparation.
Embodiment
5-bromine m-phthalic acid Zn complex of the present invention, chemical formula is:
Figure 77082DEST_PATH_IMAGE001
, 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)
Figure 649326DEST_PATH_IMAGE002
, c=21.628 (2)
Figure 411745DEST_PATH_IMAGE002
, α=90 °, β=90 °, γ=90 °, V=7657.3 (13)
Figure 531011DEST_PATH_IMAGE003
Basic structure is an interspersed network structure of three-dimensional quadruple with lfm topology, and there are two kinds of different Zn in basic structural unit 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 IIBridge linking effect by part is the three-dimensional structure with lfm topology in spatial spread.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:
Figure 986263DEST_PATH_IMAGE004
；
Wherein dpds is 4,4 '-two (4-pyridine) disulfide, and skeleton symbol is as follows:
Figure 823769DEST_PATH_IMAGE005
。
Embodiment one
With 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) with zinc acetate (24.0 mg, 0.1mmol) in water-soluble (12 mL), enclose in the reactor of 25 mL, be heated to 120 ℃ with 10 ℃ speed per hour, keep this temperature 3 days, and then naturally be cooled to room temperature, can obtain colourless bulk crystals, with this crystal separation out, through washing, drying treatment, obtain target product, productive rate about 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 one makes further characterizes as follows:
(1) crystal structure determination of title complex
The monocrystalline of choosing suitable size at room temperature carries out the 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
Figure 389880DEST_PATH_IMAGE002
), Yi φ – ω mode is collected diffraction data.The all data warp LpThe factor and experience absorption correction, crystalline structure adopt SHELXS-97 program to be solved by direct method, and hydrogen atom is synthesized by the difference fourier and is fixed on the optimum position of calculating to be determined.Use SHELX-97 program, to whole non-hydrogen atoms and anisotropy thermal parameter thereof carried out based on F 2The complete matrix least-squares refinement.Detailed axonometry data see Table 1; Important bond distance and bond angle data see Table 2.Crystalline structure is seen Fig. 1 and Fig. 2, and the topological network of title complex is seen Fig. 3.
The main crystallographic data of table 1 title complex
Figure 425969DEST_PATH_IMAGE006
Figure 989805DEST_PATH_IMAGE007
The important bond distance of table 2 (
Figure 311678DEST_PATH_IMAGE002
) and bond angle (°)
Figure 415900DEST_PATH_IMAGE008
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 seen 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 assurance, 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 about 290 ℃, has certain thermostability, for its further Application and Development as material provides the thermostability assurance, sees Fig. 6.(instrument model: SII EXStar6000 TG/DTA6300).
(5) the solid fluorescence performance study of title complex
Complex crystal sample after enrichment is processed 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 that by above-mentioned characterization result complex crystal of the present invention is characterized in that described complex crystal belongs to rhombic system, spacer is Pbca, unit cell parameters is a=20.435 (2)
Figure 572075DEST_PATH_IMAGE002
, b=17.3253 (17)
Figure 306813DEST_PATH_IMAGE002
, c=21.628 (2)
Figure 915649DEST_PATH_IMAGE002
, α=90 °, β=90 °, γ=90 °, V=7657.3 (13)
Figure 26824DEST_PATH_IMAGE003
Basic structure is an interspersed network structure of three-dimensional quadruple with lfm topology, and there are two kinds of different Zn in basic structural unit 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 IIBridge linking effect by part is the three-dimensional structure with lfm topology in spatial spread.Such three-dimensional structure and other three structures are mutually interted and are formed three-dimensional quadruple and intert network.
Embodiment two
With 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) with zinc acetate (43.2 mg, 0.18 mmol) in water-soluble (12 mL), enclose in the reactor of 25mL, be heated to 130 ℃ with 10 ℃ speed per hour, keep this temperature 3 days, and then naturally be cooled to room temperature, can obtain colourless bulk crystals, with this crystal separation out, through washing, drying treatment, obtain target product, productive rate about 52% successively.
Embodiment three
With 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) with zinc acetate (14.4 mg, 0.06 mmol) in water-soluble (12 mL), enclose in the reactor of 25mL, be heated to 130 ℃ with 10 ℃ speed per hour, keep this temperature 3 days, and then naturally be cooled to room temperature, can obtain colourless bulk crystals, with this crystal separation out, through washing, drying treatment, obtain target product, productive rate about 45% successively.
Embodiment four
With 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) with zinc acetate (28.8 mg, 0.12 mmol) in water-soluble (12 mL), enclose in the reactor of 25mL, be heated to 160 ℃ with 10 ℃ speed per hour, keep this temperature 3 days, and then naturally be cooled to room temperature, can obtain colourless bulk crystals, with this crystal separation out, through washing, drying treatment, obtain target product, productive rate about 47% successively.
Above embodiment only is used for content of the present invention is described that in addition, the present invention also has other embodiment.But all employings are equal to replaces or technical scheme that the equivalent deformation mode forms all drops in protection scope of the present invention.

Claims (4)

1. 5-bromine m-phthalic acid Zn complex, it is characterized in that: the chemical formula of described 5-bromine m-phthalic acid Zn complex is:
Figure 144324DEST_PATH_IMAGE001
, 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)
Figure 223138DEST_PATH_IMAGE002
, b=17.3253 (17) , c=21.628 (2)
Figure 164866DEST_PATH_IMAGE002
, α=90 °, β=90 °, γ=90 °, V=7657.3 (13)
Figure 315837DEST_PATH_IMAGE003
Wherein L is 5-bromine m-phthalic acid anion ligand, and skeleton symbol is as follows:
Figure 198343DEST_PATH_IMAGE004
；
Wherein dpds is 4,4 '-two (4-pyridine) disulfide, and skeleton symbol is as follows:
Figure 550827DEST_PATH_IMAGE005
。
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, 5-bromine m-phthalic acid, mineral alkali, dpds and zinc salt is soluble in water, and in the inclosure reactor, be heated to 120 ~ 160 ℃ with 10 ℃ temperature rise rate per hour, be incubated afterwards 3 days, then natural condition drop to room temperature, can obtain colourless bulk crystals, the successively process washing of colourless bulk crystals, drying treatment with collecting obtain target product;
The zinc salt of the 5-bromine m-phthalic acid of per 1 L water adding, 0.005 ~ 0.015 mol, dpds, 0.005 ~ 0.015 mol of 0.005 ~ 0.015 mol and the mineral alkali of 0.005 ~ 0.015 mol.
3. the preparation method of 5-bromine m-phthalic acid Zn complex as claimed in claim 2, it is characterized in that: described zinc salt is zinc acetate or zinc perchlorate.
4. the preparation method of 5-bromine m-phthalic acid Zn complex as claimed in claim 2 or claim 3, it is characterized in that: described mineral alkali is potassium hydroxide or sodium hydroxide.
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CN104086575A (en) * 2014-06-25 2014-10-08 河南工程学院 Bis(pyridine)-(4-hydroxybenzoic acid)-chloro-zinc(II) complex and preparation method thereof
CN105001247A (en) * 2015-07-15 2015-10-28 洛阳师范学院 4-bromoisophthalic acid and 1,4-bis(imidazole-1-methylene group)benzene blending cadmium complex and preparation method
CN105801607A (en) * 2016-04-19 2016-07-27 赖树兴 Novel 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
CN107556489A (en) * 2017-10-16 2018-01-09 山东理工大学 A kind of spin crossover molecular magnetic materialses of Stress control and preparation method thereof

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CN102584866A (en) * 2012-01-18 2012-07-18 郑州轻工业学院 1,2-naphthalene diacid containing cadmium coordination complex and preparation method thereof
CN102584865A (en) * 2012-01-30 2012-07-18 东华理工大学 Preparation method of zinc complex with light emitting adjustability and white light emitting property

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CN101993421A (en) * 2009-08-25 2011-03-30 中国科学院福建物质结构研究所 Synthesis and application of blue-fluorescence luminous zinc metal complex
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104086575A (en) * 2014-06-25 2014-10-08 河南工程学院 Bis(pyridine)-(4-hydroxybenzoic acid)-chloro-zinc(II) complex and preparation method thereof
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CN105001247A (en) * 2015-07-15 2015-10-28 洛阳师范学院 4-bromoisophthalic acid and 1,4-bis(imidazole-1-methylene group)benzene blending cadmium complex and preparation method
CN105801607A (en) * 2016-04-19 2016-07-27 赖树兴 Novel PVC heat stabilizer and preparation method thereof
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
CN107556489A (en) * 2017-10-16 2018-01-09 山东理工大学 A kind of spin crossover molecular magnetic materialses of Stress control and preparation method thereof
CN107556489B (en) * 2017-10-16 2020-06-19 山东理工大学 Pressure-controlled spin cross molecular magnetic material and preparation method thereof

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