CN110330527A - A kind of mononuclear copper complex and preparation method thereof with fluorescence property - Google Patents
A kind of mononuclear copper complex and preparation method thereof with fluorescence property Download PDFInfo
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- CN110330527A CN110330527A CN201910774963.XA CN201910774963A CN110330527A CN 110330527 A CN110330527 A CN 110330527A CN 201910774963 A CN201910774963 A CN 201910774963A CN 110330527 A CN110330527 A CN 110330527A
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
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- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
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Abstract
The invention discloses a kind of mononuclear copper complex and preparation method thereof with fluorescence property, the molecular formula of complex are C63H51CuClN3O2P2, the crystal of the complex belongs to anorthic system, cell parameter are as follows: α=79.21 °, β=87.78 °, γ=86.12 °；It include a copper ion, a benzimidazole phosphine ligand and a triphenylphosphine assistant ligand in each complex molecule；In crystal, complex center Cu ion is coordinated with the P atom in N, P atom and assistant ligand triphenylphosphine in Cl ion and benzimidazole phosphine ligand respectively, forms the distorted tetrahedral configuration of four-coordination.Invention also provides the preparation method of the complex, this method reaction condition is mild, and preparation process is simple, low in cost, has preferable thermal stability while gained copper complex is with fluorescence property.
Description
Technical field
The invention belongs to metal organic complex synthesis technical fields, and in particular to a kind of monokaryon copper with fluorescence property
Complex and preparation method thereof.
Background technique
Important research theme one of of the metal organic complex as current materials chemistry not only has aesthetics of structural design valence
Value, and have a good application prospect in fields such as luminous, magnetism, absorption, hydrogen storage, catalysis and separation.Especially by gold
Belong to the coordination of ion and organic multi-functional ligand to construct the coordination polymerization with high thermal stability structure and extraordinary physical and chemical performance
Object has caused the great interest of people.However it designs and constructs this kind of material with special construction and function and belong to innovation
Technology has very big challenge, especially has both the material of preferable thermal stability and optical property.In recent years, some to have
High thermal stability, or the coordination polymer with fluorescence property have been widely studied, and achieve certain achievement, but at this
In a little complexs, while the material for having both preferable thermal stability and fluorescence property is but rarely reported.
Summary of the invention
To overcome problem above, the present invention provides a kind of mononuclear copper complex and preparation method thereof with fluorescence property,
This method reaction condition is mild, and preparation process is simple, low in cost, and gained mononuclear copper complex has preferable fluorescence simultaneously
Energy and thermal stability.
The object of the invention to solve the technical problems adopts the following technical solutions to realize.It proposes according to the present invention
A kind of mononuclear copper complex with fluorescence property, molecular formula C61H47CuClN3O2P2, the crystal of the complex belongs to
Anorthic system, cell parameter are as follows: α=79.21 °, β=
87.78 °, γ=86.12 °；Include a copper ion, a benzimidazole phosphine ligand and one in each complex molecule
Triphenylphosphine assistant ligand；In crystal, the Cu ion at complex center is respectively and in Cl ion and benzimidazole phosphine ligand
N, P atom and assistant ligand triphenylphosphine in P atom be coordinated, form the distorted tetrahedral configuration of four-coordination.
Further, the structural formula of the benzimidazole phosphine ligand are as follows:
Further, the structural formula of the mononuclear copper complex are as follows:
Mononuclear copper complex above-mentioned with fluorescence property, the application in optical material.
The object of the invention to solve the technical problems also can be used following technical scheme and further realize.One kind has glimmering
The preparation method of the mononuclear copper complex of optical property, comprising the following steps:
(1) 2~3mmol stannous chloride, 2~3mmol benzimidazole phosphine ligand and 2~3mmol triphenylphosphine are added
To in the mixed solution of 20~25ml methylene chloride and acetonitrile, heats the mixture to 40-50 DEG C and constantly stir at such a temperature
Mix holding 2~3 hours；
The structural formula of the benzimidazole phosphine ligand are as follows:
(2) step (1) reacted solution is filtered and transferred in 30ml vial, volatilization 72~96 is small naturally
When, complex crystal is obtained, crystal is filtered out, is washed with acetonitrile, vacuum drying obtains final products-mononuclear copper complex；
The structural formula of gained mononuclear copper complex are as follows:
Further, stannous chloride described in step (1) and the substance of benzimidazole phosphine ligand and triphenylphosphine
The ratio between amount is 1:1:1.
Further, the volume ratio of methylene chloride and acetonitrile is 4:1 in step (1).
Compared with prior art, the invention has the following advantages that
(1) mononuclear copper complex of the invention have stronger fluorescence, complex during the preparation process, directly by ligand
It is reacted to obtain with stannous chloride, gained mononuclear copper complex occurs under the conditions of excitation spectrum is λ ex=400nm and 293K
Strong emission peak λ em=603nm, its fluorescent emission may be mainly due to the electron transmission between central atom-ligand
(MLCT) fluorescence caused by effect；
(2) the TG curve of mononuclear copper complex of the invention shows that organic ligand is weightless since 268.5 DEG C, causes to tie
Structure frame collapses, and illustrates that the mononuclear copper complex has preferable thermal stability；
(3) preparation process of copper complex of the present invention is simple, and high production efficiency, equipment investment is few, while entirely producing
Journey pollution is few, meets sustainable development requirement.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
It can be implemented in accordance with the contents of the specification, and in order to allow above and other objects, features and advantages of the invention can be more
It becomes apparent, special below to lift preferred embodiment, detailed description are as follows.
Detailed description of the invention
Fig. 1 is mononuclear copper complex C of the present invention61H47CuClN3O2P2Crystal structure do not shown in Fig. 1 to be high-visible
Show the hydrogen atom in structure.
Fig. 2 is mononuclear copper complex C of the present invention61H47CuClN3O2P2TG curve.
Fig. 3 is mononuclear copper complex C of the present invention61H47CuClN3O2P2Solid fluorescence emission spectrum at room temperature 293K
Figure.
Fig. 4 is mononuclear copper complex C of the present invention61H47CuClN3O2P2Synthetic route chart.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Attached drawing and preferred embodiment, to a kind of mononuclear copper complex of fluorescence property proposed according to the present invention and preparation method thereof,
Specific embodiment, feature and its effect, detailed description is as follows.
Embodiment 1
At room temperature, 0.198g (2mmol) stannous chloride, 1.307g (2mmol) benzimidazole phosphine ligand are weighed
It is added in the mixed solution of 20ml methylene chloride and acetonitrile (methylene chloride and acetonitrile with 0.524g (3mmol) triphenylphosphine
Volume ratio=4:1), it is heated to 45 DEG C and is stirred continuously holding 2 hours at such a temperature.Reacted solution is filtered and shifted
Into 30ml vial, volatilizees 72 hours naturally, obtains complex crystal, filter out crystal, washed with a small amount of acetonitrile,
Vacuum drying obtains final products, yield 75%.
Embodiment 2
At room temperature, 0.297g (3mmol) stannous chloride, 2.045g (3mmol) benzimidazole phosphine ligand are weighed
It is added in the mixed solution of 25ml methylene chloride and acetonitrile (methylene chloride and acetonitrile with 0.786g (3mmol) triphenylphosphine
Volume ratio=4:1), it is heated to 45 DEG C and is stirred continuously holding 3 hours at such a temperature.Reacted solution is filtered and shifted
Into 30ml vial, volatilizees 96 hours naturally, obtains complex crystal, filter out crystal, washed with a small amount of acetonitrile,
Vacuum drying obtains final products, yield 76%.
Benzimidazole phosphine ligand structure formula used in embodiment 1 and embodiment 2 are as follows:
The benzimidazole phosphine ligand reacts final according to reaction principle shown in Fig. 4 with triphenylphosphine and stannous chloride
The structural formula of obtained mononuclear copper complex is as follows:
Characterization detection is carried out to coordination polymer obtained by embodiment 1 and embodiment 2:
(1) crystal structure
The monocrystalline for choosing suitable size under the microscope is spread out using II CCD X-ray monocrystalline of Bruker AMART APEX
Penetrate instrument (graphite monochromator Mo-K α radiation,) ω/θ scanning mode collection X-ray monocrystalline is used at 150K
Data.Structure elucidation is carried out by SHELXS-97, and is used
SHELXL-97 program bag carries out refinement refine by complete matrix least square method, adds hydrogen in suitable position theory, right
All non-hydrogen atoms use anisotropy refine.The crystal structure of the complex is shown in Fig. 1, the partial parameters of crystallographic structure refine
It see the table below 1:
The crystallography point diffraction data collection and structure refinement parameter of 2 gained complex of 1. embodiment 1 of table and embodiment
(2) differential thermal thermogravimetric analysis characterizes
Using the resistance to 449 F1 type synchronous solving of TG-DSC STA of speeding of Germany, with α-Al2O3For reference substance, in 300ml/
The stream of nitrogen gas of min is protected, and heating rate measures the TG curve of complex under conditions of being 10 DEG C/min.The TG of the complex is bent
Line causes frame structure to be collapsed as shown in Fig. 2, organic ligand weightlessness since 268.5 DEG C, and it is preferable to illustrate that gained complex has
Thermal stability.
(3) solid powder luminosity
Solid powder luminosity is measured using 2015 FS5 type integration Fluorescence Spectrometer of Edinburg BCEIA, the cooperation
The solid powder luminescent spectrum of object is as shown in figure 3, gained complex in excitation spectrum is λexUnder conditions of=400nm, in 293K
When complex maximum emission wavelength be 603nm, its fluorescent emission may be mainly due to the electronics between central atom-ligand biography
Pass fluorescence caused by (MLCT) effect.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, this
The preferred embodiment of invention is not intended to limit the invention, any person skilled in the art, is not departing from skill of the present invention
In the range of art scheme, according to the technical essence of the invention it is to the above embodiments it is any it is simple modification, equivalent variations with
Modification, all of which are still within the scope of the technical scheme of the invention.
Claims (7)
1. a kind of mononuclear copper complex with fluorescence property, it is characterised in that: its molecular formula is C61H47CuClN3O2P2, this is matched
The crystal for closing object belongs to anorthic system, cell parameter are as follows: α=
79.21 °, β=87.78 °, γ=86.12 °；It include a copper ion, a benzimidazole phosphine in each complex molecule
Ligand and a triphenylphosphine assistant ligand；In crystal, the Cu ion at complex center respectively with Cl ion and benzimidazole
The P atom in N, P atom and assistant ligand triphenylphosphine in phosphine ligand is coordinated, and the distorted tetrahedral of four-coordination is formed
Body configuration.
2. as described in claim 1 with the mononuclear copper complex of fluorescence property, it is characterised in that: the benzimidazole phosphine
The structural formula of class ligand are as follows:
。
3. as described in claim 1 with the mononuclear copper complex of fluorescence property, it is characterised in that: the mononuclear copper complex
Structural formula are as follows:
。
4. as described in claim 1 with the mononuclear copper complex of fluorescence property, the application in optical material.
5. a kind of preparation method of the mononuclear copper complex with fluorescence property, it is characterised in that the following steps are included:
(1) 2~3mmol stannous chloride, 2~3mmol benzimidazole phosphine ligand and 2~3mmol triphenylphosphine are added to 20
In the mixed solution of~25ml methylene chloride and acetonitrile, heats the mixture to 40-50 DEG C and be stirred continuously guarantor at such a temperature
It holds 2~3 hours；
The structural formula of the benzimidazole phosphine ligand are as follows:
(2) step (1) reacted solution is filtered and transferred in 30ml vial, volatilizees 72~96 hours, obtains naturally
To complex crystal, crystal is filtered out, is washed with acetonitrile, vacuum drying obtains final products-mononuclear copper complex；
The structural formula of gained mononuclear copper complex are as follows:
。
6. the preparation method of the mononuclear copper complex with fluorescence property as claimed in claim 5, it is characterised in that step (1)
Described in stannous chloride and the ratio between the amount of substance of benzimidazole phosphine ligand and triphenylphosphine be 1:1:1.
7. the preparation method of the mononuclear copper complex with fluorescence property as claimed in claim 5, it is characterised in that step (1)
The volume ratio of middle methylene chloride and acetonitrile is 4:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112010904A (en) * | 2020-09-02 | 2020-12-01 | 洛阳理工学院 | Benzimidazole diphosphine Cu (I) complex and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016012221A2 (en) * | 2014-07-21 | 2016-01-28 | Cynora Gmbh | Organic component |
| CN105924469A (en) * | 2016-04-18 | 2016-09-07 | 中国计量大学 | Crystalline benzimidazolyl quinoline cuprous complex luminescent material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016012221A2 (en) * | 2014-07-21 | 2016-01-28 | Cynora Gmbh | Organic component |
| CN105924469A (en) * | 2016-04-18 | 2016-09-07 | 中国计量大学 | Crystalline benzimidazolyl quinoline cuprous complex luminescent material |
Non-Patent Citations (1)
| Title |
|---|
| 张斌: ""新型苯并咪唑衍生物的合成及金属离子调控的发光性质研究"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112010904A (en) * | 2020-09-02 | 2020-12-01 | 洛阳理工学院 | Benzimidazole diphosphine Cu (I) complex and preparation method thereof |
| CN112010904B (en) * | 2020-09-02 | 2021-07-20 | 洛阳理工学院 | Benzimidazole diphosphine Cu (I) complex and preparation method thereof |
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