CN103755633A - 8-aminoquinoline zinc perchlorate metal complex, and preparation method and application thereof - Google Patents
8-aminoquinoline zinc perchlorate metal complex, and preparation method and application thereof Download PDFInfo
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- CN103755633A CN103755633A CN201410036268.0A CN201410036268A CN103755633A CN 103755633 A CN103755633 A CN 103755633A CN 201410036268 A CN201410036268 A CN 201410036268A CN 103755633 A CN103755633 A CN 103755633A
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- quinolylamine
- zinc perchlorate
- metal complexes
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages
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- 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
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Abstract
The invention discloses 8-aminoquinoline zinc perchlorate metal complexes, and a preparation method and application thereof. Zn(ClO4)2 and 8-aminoquinoline are respectively dissolved in methanol solvents to prepare two solutions; then the two solutions are mixed, the obtained mixed solution is refluxed under stirring, and is filtered; filtrate is subjected to extraction in non-polar solvents; two weeks later, complex monocrystal of which the molecular formula is C18H16C12N4O8Zn is obtained. The complexes form three-dimensional supermolecular structures via accumulation of hydrogen bonds and pi...pi-bond aromatic nucleus. The test with a fluorospectrophotometer shows that the complexes have excellent fluorescence property and can be used as luminescent materials.
Description
Technical field
The invention belongs to organic synthesis field, relate to a kind of 8-quinolylamine zinc perchlorate metal complexes and monocrystalline and preparation method, and this title complex is as the application of luminescent material aspect.
Background technology
A metal-organic complex fluorescent material has potential using value in fields such as communication, satellite, radar, optical computer, novel battery and probe biomolecules, is the important component part of molecular material family.The molecular designing of the functional title complex of this class, synthetic and property research are all subject to extensive concern all the time.The luminescent properties of the molecular luminescence material consisting of functional molecular depends on the coordination situation of part and metal ion to a great extent.And the chelate effect that aromatic nucleus and metal ion form is by the efficiency of very big strongthener emitting fluorescence.For this reason, selecting 8-quinolylamine is that a metal-organic complex that organic ligand and metallic ion coordination form is the preferred material in this field.
Summary of the invention
First object of the present invention is to provide a kind of 8-quinolylamine zinc perchlorate metal complexes.This title complex is by hydrogen bond and π ... π aromatic nucleus is piled up and is formed Magnetic Properties of Three-Dimensional Supramolecular Complex structure and have good fluorescence property, can be used as potential luminescent material application.
The chemical formula of 8-quinolylamine zinc perchlorate metal complexes involved in the present invention is (L
1)
2zn (ClO
4)
2, L wherein
1for 8-quinolylamine.
Second object of the present invention is to provide a kind of preparation method of 8-quinolylamine zinc perchlorate metal complexes.
For achieving the above object, the preparation method of 8-quinolylamine zinc perchlorate metal complexes of the present invention is: with Zn (ClO
4)
2with L
1mol ratio be 1: 2, by Zn (ClO
4)
2and L
1all be dissolved in methanol solvate, stir lower backflow; Filter, filtrate extracts in nonpolar extraction solvent, obtains clear crystal after fortnight, filters, and ether washing leaching cake, obtains target title complex; Described L
1for 8-quinolylamine.
The time of refluxing under described stirring is 2～6 hours.
Described extraction solvent is ether or tetracol phenixin.
It is construction unit that the present invention selects zinc perchlorate, using can form hydrogen bond 8-quinolylamine as bidentate ligand, carry out self-assembly, obtain having Magnetic Properties of Three-Dimensional Supramolecular Complex structure and epipolic Metal-organic complex monocrystalline.Their secondary building unit is: crystal belongs to triclinic(crystalline)system, and spacer is P-1, and unit cell parameters is:
α=74.9950 (10) °, β=77.4690 (10) °, γ=70.8460 (10) °.In the asymmetric cell of this title complex, contain 1 Zn
2+, 2 L
1part and 2 ClO
4 -.Each Zn
2+with come from two L
14 N atoms of part and come from two ClO
4 -2 O Atomic coordinates, form the octahedral coordination geometric configuration of distortion.Intermolecular weak hydrogen bond and π ... π aromatic nucleus is piled up and is formed Magnetic Properties of Three-Dimensional Supramolecular Complex structure.Wherein, octahedral Zn-N bond distance is
zn-O bond distance is
N-Zn-N bond angle numerical value is respectively 81.03 (7) °, 98.97 (7) ° and 180.0 °.O-Zn-O bond angle numerical value is 180.00 (8) °.Preparation method of the present invention is simple, and raw material is easy to get, and this title complex has Magnetic Properties of Three-Dimensional Supramolecular Complex structure.
The 3rd object of the present invention is to provide a kind of 8-quinolylamine zinc perchlorate metal complexes as the application of luminescent material aspect.
Accompanying drawing explanation
Fig. 1 is the crystalline structure figure of 8-quinolylamine zinc perchlorate metal complexes of the present invention;
Fig. 2 is the packed structures figure of 8-quinolylamine zinc perchlorate metal complexes of the present invention;
Fig. 3 is the Solid fluorescene spectrum figure of 8-quinolylamine zinc perchlorate metal complexes of the present invention.
Embodiment
The chemical formula of 8-quinolylamine zinc perchlorate metal complexes of the present invention is (L
1)
2zn (ClO
4)
2, L wherein
1for 8-quinolylamine.
Below in conjunction with concrete embodiment, further set forth the present invention.
Embodiment 1:0.05mmol Zn (ClO
4)
2(13.2mg) with 0.10mmol L
1(14.4mg) be dissolved in respectively in 10ml methanol solvate, under room temperature condition, two kinds of solution phases mixed, stir lower backflow 2 hours, filter, filtrate is placed in 50ml beaker, with film seal, and pricks aperture, is placed in ether pond and extracts.After fortnight, obtain clear crystal, filter, filter cake washs with ether, obtains target title complex, based on Zn (ClO
4)
2the productive rate calculating is 51%.
Embodiment 2:0.05mmol Zn (ClO
4)
2(13.2mg) with 0.10mmol L
1(14.4mg) be dissolved in respectively in 10ml methanol solvate, under room temperature condition, two kinds of solution phases mixed, stir lower backflow 4 hours, filter, filtrate is placed in 50ml beaker, with film seal, and pricks aperture, is placed in ether pond and extracts.After fortnight, obtain clear crystal, filter, filter cake washs with ether, obtains target title complex, based on Zn (ClO
4)
2the productive rate calculating is 67%.
Embodiment 3:0.05mmol Zn (ClO
4)
2(13.2mg) with 0.10mmol L
1(14.4mg) be dissolved in respectively in 10ml methanol solvate, under room temperature condition, two kinds of solution phases mixed, stir lower backflow 4 hours, filter, filtrate is placed in 50ml beaker, with film seal, and pricks aperture, is placed in tetracol phenixin pond and extracts.After fortnight, obtain clear crystal, filter, filter cake washs with ether, obtains target title complex, based on Zn (ClO
4)
2the productive rate calculating is 35%.
Embodiment 4:0.05mmol Zn (ClO
4)
2(13.2mg) with 0.10mmol L
1(14.4mg) be dissolved in respectively in 10ml methanol solvate, under room temperature condition, two kinds of solution phases mixed, stir lower backflow 6 hours, filter, filtrate is placed in 50ml beaker, with film seal, and pricks aperture, is placed in tetracol phenixin pond and extracts.After fortnight, obtain clear crystal, filter, filter cake washs with ether, obtains target title complex, based on Zn (ClO
4)
2the productive rate calculating is 54%.
Embodiment 5: luminescent material, and concrete method steps is as follows:
By spectrophotofluorometer, carry out respectively the excitation wavelength of 8-quinolylamine zinc perchlorate metal complexes and the scanning of emission wavelength, select and definite optimal wavelength.
Conclusion: the excitation wavelength of this title complex and emission wavelength are respectively 340.0nm and 521.8nm.
The structure determination of 8-quinolylamine zinc perchlorate metal complexes of the present invention:
Crystalline structure adopts Bruker Smart Apex II CCD single crystal diffractometer to measure, with the Mok alpha-ray of graphite monochromatization (
for incident radiation, ω-2 θ scan mode is collected room temperature X-ray single crystal diffraction data, method of least squares refine unit cell parameters, SHELXL-97 direct method solves crystalline structure, and complete matrix least square square law carries out refine to all non-hydrogen atoms position and anisotropic thermal temperature factor.All H atom sites are determined by how much hydrogenation modes.Detailed axonometry data are in Table 1, and structure is shown in Fig. 1 and 2, and fluorescence spectrum is shown in Fig. 3.
The crystallographic data of table 1 8-quinolylamine of the present invention zinc perchlorate metal complexes
Claims (6)
1.8-quinolylamine zinc perchlorate metal complexes has following structure:
2.8-quinolylamine zinc perchlorate metal complexes monocrystalline, is characterized in that this single crystal structure adopts the SMART CCD area detector diffractometer with graphite monochromator, and X-ray source is MoK α
with ω-2 θ scan mode, collect point diffraction, through least-squares refinement, obtain unit cell parameters, diffraction data is processed with SAINT programe reduction, and crystallographic structural analysis is used SHELXL-97 software package, and solves monocrystalline data by heavy atom method:
3. a complex preparation method as claimed in claim 1, is characterized in that: with Zn (ClO
4)
2with the mol ratio of 8-quinolylamine be 1: 2, by Zn (ClO
4)
2be dissolved in respectively in methanol solvate with 8-quinolylamine, above-mentioned two kinds of solution are mixed, stir lower backflow; Filter, filtrate extracts in nonpolar extraction solvent, obtains clear crystal after fortnight, filters, and ether washing leaching cake, obtains target title complex.
4. complex preparation method as claimed in claim 3, is characterized in that: the time of refluxing under described stirring is 2～6 hours.
5. complex preparation method as claimed in claim 3, is characterized in that: described extraction solvent is ether or tetracol phenixin.
6.8-quinolylamine zinc perchlorate metal complexes is in the application of preparing aspect luminescent material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583947A (en) * | 2004-06-07 | 2005-02-23 | 中国科学院广州化学研究所 | Luminescent polymer materials containing 8-hydroxy quinoline metal complex and their preparation and use |
| CN101041667A (en) * | 2007-04-30 | 2007-09-26 | 中国科学院广州化学研究所 | Bipolar compound containing 8-hydroxyquinoline metal complex and preparation method thereof |
| CN103509041A (en) * | 2013-10-13 | 2014-01-15 | 安庆师范学院 | Cadmium perchlorate-8-aminoquinoline complex and preparation method thereof |
-
2014
- 2014-01-21 CN CN201410036268.0A patent/CN103755633B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583947A (en) * | 2004-06-07 | 2005-02-23 | 中国科学院广州化学研究所 | Luminescent polymer materials containing 8-hydroxy quinoline metal complex and their preparation and use |
| CN101041667A (en) * | 2007-04-30 | 2007-09-26 | 中国科学院广州化学研究所 | Bipolar compound containing 8-hydroxyquinoline metal complex and preparation method thereof |
| CN103509041A (en) * | 2013-10-13 | 2014-01-15 | 安庆师范学院 | Cadmium perchlorate-8-aminoquinoline complex and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 徐衡等: "8-氨基喹啉镉配合物溶液的荧光性质", 《光谱实验室》, vol. 29, no. 5, 30 September 2012 (2012-09-30), pages 3238 - 3241 * |
| 郭丽敏: "8-氨基喹啉镉、锌配合物：合成、结构和光谱性质", 《安徽师范大学硕士学位论文》, 15 June 2008 (2008-06-15) * |
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