CN110330527B - Mononuclear copper complex with fluorescence property and preparation method thereof - Google Patents

Mononuclear copper complex with fluorescence property and preparation method thereof Download PDF

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CN110330527B
CN110330527B CN201910774963.XA CN201910774963A CN110330527B CN 110330527 B CN110330527 B CN 110330527B CN 201910774963 A CN201910774963 A CN 201910774963A CN 110330527 B CN110330527 B CN 110330527B
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complex
crystal
copper complex
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triphenylphosphine
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尹国杰
张斌
焦冰晶
杜晨霞
张琳
李冬
杨刚宾
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Luoyang Institute of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • 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
    • C07F9/50—Organo-phosphines
    • C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • C07B2200/13—Crystalline forms, e.g. polymorphs
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    • 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 a mononuclear copper complex with fluorescence property and a preparation method thereof, wherein the molecular formula of the complex is C63H51CuClN3O2P2The crystal of the complex belongs to a triclinic crystal system, and the unit cell parameters are as follows:
Figure DDA0002174740960000011
Figure DDA0002174740960000012
α is 79.21 °, β is 87.78 °, γ is 86.12 °; each complex molecule contains a copper ion, a benzimidazole phosphine ligand and a triphenylphosphine auxiliary ligand; in the crystal, Cu ions at the center of the complex are respectively coordinated with Cl ions, N, P atoms in benzimidazole phosphine ligands and P atoms in auxiliary ligands, namely triphenylphosphine, so that a four-coordination distorted tetrahedral configuration is formed. The invention also provides a preparation method of the complex, the method has mild reaction conditions, simple preparation process and low cost, and the obtained copper complex has fluorescence property and better thermal stability.

Description

Mononuclear copper complex with fluorescence property and preparation method thereof
Technical Field
The invention belongs to the technical field of metal organic complex synthesis, and particularly relates to a mononuclear copper complex with fluorescence property and a preparation method thereof.
Background
The metal organic complex is one of the important research subjects of the current material chemistry, has structural aesthetic value, and has good application prospect in the fields of luminescence, magnetism, adsorption, hydrogen storage, catalysis, separation and the like. Particularly, the coordination polymer with high thermal stability structure and special physicochemical property constructed by coordination of metal ions and organic multifunctional ligand has attracted great interest. However, designing and constructing such materials with special structures and functions is an innovative technology and has great challenges, especially for materials with good thermal stability and optical properties. In recent years, some coordination polymers with high thermal stability or fluorescent property have been extensively studied and have achieved certain results, but in these complexes, materials with both good thermal stability and fluorescent property are rarely reported.
Disclosure of Invention
In order to overcome the problems, the invention provides the mononuclear copper complex with the fluorescence property and the preparation method thereof.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The invention provides a mononuclear copper complex with fluorescent property, and the molecular formula of the mononuclear copper complex is C61H47CuClN3O2P2The crystal of the complex belongs to a triclinic crystal system, and the unit cell parameters are as follows:
Figure BDA0002174740940000011
Figure BDA0002174740940000012
α is 79.21 °, β is 87.78 °, γ is 86.12 °; each complex molecule contains a copper ion, a benzimidazole phosphine ligand and a triphenylphosphine auxiliary ligand; in the crystal, Cu ions in the center of the complex are respectively coordinated with Cl ions, N, P atoms in benzimidazole phosphine ligands and P atoms in auxiliary ligands, namely triphenylphosphine, so that a four-coordination distorted tetrahedral configuration is formed.
Further, the structural formula of the benzimidazole phosphine ligand is as follows:
Figure BDA0002174740940000021
further, the mononuclear copper complex has a structural formula:
Figure BDA0002174740940000022
the mononuclear copper complex with the fluorescent property is applied to optical materials.
The purpose of the invention and the technical problem to be solved can be further realized by adopting the following technical scheme. A preparation method of a mononuclear copper complex with fluorescent property comprises the following steps:
(1) adding 2-3 mmol of cuprous chloride, 2-3 mmol of benzimidazolephosphine ligand and 2-3 mmol of triphenylphosphine into 20-25 ml of mixed solution of dichloromethane and acetonitrile, heating the mixture to 40-50 ℃, and continuously stirring and keeping for 2-3 hours at the temperature;
the structural formula of the benzimidazole phosphine ligand is as follows:
Figure BDA0002174740940000023
(2) filtering the solution reacted in the step (1), transferring the solution into a 30ml glass bottle, naturally volatilizing for 72-96 hours to obtain a complex crystal, filtering the crystal, washing with acetonitrile, and drying in vacuum to obtain a final product, namely a mononuclear copper complex;
the structural formula of the obtained mononuclear copper complex is as follows:
Figure BDA0002174740940000031
further, the ratio of the cuprous chloride to the amounts of the benzimidazolphosphine ligand and the triphenylphosphine in the step (1) is 1:1: 1.
Further, the volume ratio of dichloromethane to acetonitrile in step (1) is 4: 1.
Compared with the prior art, the invention has the following advantages:
(1) the mononuclear copper complex has stronger fluorescence, the complex is obtained by directly reacting a ligand with cuprous chloride in the preparation process, the obtained mononuclear copper complex has a strong emission peak lambda em of 603nm under the conditions that the excitation spectrum is lambda ex of 400nm and 293K, and the fluorescence emission of the mononuclear copper complex is probably mainly caused by the electron transfer (MLCT) action between a central atom and the ligand;
(2) the TG curve of the mononuclear copper complex shows that the organic ligand starts to lose weight from 268.5 ℃ to cause structural framework collapse, which indicates that the mononuclear copper complex has better thermal stability;
(3) the preparation process of the copper complex is simple, the production efficiency is high, the equipment investment is low, the pollution in the whole production process is low, and the sustainable development requirement is met.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more apparent, the following specific preferred embodiments are described in detail.
Drawings
FIG. 1 shows a mononuclear copper complex C according to the invention61H47CuClN3O2P2The crystal structure of (a) is not shown in fig. 1 for clarity of visualization.
FIG. 2 shows a mononuclear copper complex C according to the present invention61H47CuClN3O2P2The TG curve of (1).
FIG. 3 shows a mononuclear copper complex C according to the present invention61H47CuClN3O2P2And a solid fluorescence emission spectrum at room temperature of 293K.
FIG. 4 shows a mononuclear copper complex C according to the present invention61H47CuClN3O2P2Synthetic route maps of (1).
Detailed Description
To further illustrate the technical means and effects of the present invention for achieving the predetermined objects, the following detailed description of the fluorescent mononuclear copper complex and the preparation method thereof according to the present invention, the specific embodiments, features and effects thereof are described in detail with reference to the accompanying drawings and preferred embodiments.
Example 1
0.198g (2mmol) of cuprous chloride, 1.307g (2mmol) of a benzimidazolphosphine ligand and 0.524g (3mmol) of triphenylphosphine were weighed into a 20ml mixed solution of dichloromethane and acetonitrile (the volume ratio of dichloromethane to acetonitrile was 4:1) at room temperature, heated to 45 ℃ and kept at the temperature for 2 hours with continuous stirring. And filtering the reacted solution, transferring the solution into a 30ml glass bottle, naturally volatilizing for 72 hours to obtain a complex crystal, filtering the complex crystal, washing the crystal with a small amount of acetonitrile, and drying in vacuum to obtain a final product with the yield of 75%.
Example 2
0.297g (3mmol) of cuprous chloride, 2.045g (3mmol) of a benzimidazol phosphine-based ligand and 0.786g (3mmol) of triphenylphosphine were weighed out at room temperature into 25ml of a mixed solution of dichloromethane and acetonitrile (the volume ratio of dichloromethane to acetonitrile was 4:1), heated to 45 ℃ and kept at that temperature for 3 hours with continuous stirring. And filtering the reacted solution, transferring the solution into a 30ml glass bottle, naturally volatilizing for 96 hours to obtain a complex crystal, filtering the complex crystal, washing the crystal with a small amount of acetonitrile, and drying in vacuum to obtain a final product with the yield of 76%.
The benzimidazole phosphine ligands used in examples 1 and 2 have the structural formula:
Figure BDA0002174740940000041
the structural formula of the mononuclear copper complex finally obtained by reacting the benzimidazole phosphine ligand with triphenylphosphine and cuprous chloride according to the reaction principle shown in figure 4 is as follows:
Figure BDA0002174740940000051
characterization tests were carried out on the coordination polymers prepared in example 1 and example 2:
(1) crystal structure
Single crystals of appropriate size were selected under a microscope and analyzed using a Bruker amar APEX ii CCD X-ray single crystal diffractometer (graphite monochromator Mo-K alpha radiation,
Figure BDA0002174740940000053
) X-ray single crystal data was collected using a omega/theta scanning mode at 150K. Structural resolution by SHELXS-97 and use
The SHELXL-97 package is refined by a full matrix least square method, theoretically hydrogenated at a proper position, and refined anisotropically to all non-hydrogen atoms. The crystal structure of the complex is shown in figure 1, and partial parameters of the refined crystal structure are shown in the following table 1:
TABLE 1 crystallographic diffraction Point data Collection and Structure refinement parameters for the complexes obtained in examples 1 and 2
Figure BDA0002174740940000052
Figure BDA0002174740940000061
(2) Differential thermal thermogravimetric analysis characterization
Adopting German relaxation-resistant TG-DSC STA 449F 1 type synchronous thermal analyzer to analyze alpha-Al2O3As a reference substance, the TG curve of the complex was determined under the protection of a nitrogen stream of 300ml/min and at a temperature rise rate of 10 ℃/min. The TG curve of the complex is shown in figure 2, and the organic ligand starts to lose weight from 268.5 ℃ so as to cause the collapse of a framework structure, which indicates that the obtained complex has better thermal stability.
(3) Luminescence property of solid powder
The luminescence property of the solid powder is measured by an Edinburgh BCEIA 2015 FS5 type integrated fluorescence spectrometer, and the luminescence spectrum of the solid powder of the complex isAs shown in FIG. 3, the resulting complex had an excitation spectrum of λexUnder the condition of 400nm, the maximum emission wavelength of the complex at 293K is 603nm, and the fluorescence emission of the complex is probably mainly attributed to fluorescence caused by electron transfer (MLCT) between central atom and ligand.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention in any way, and any simple modifications, equivalent variations and modifications made by those skilled in the art without departing from the scope of the present invention shall fall within the scope of the present invention.

Claims (1)

1. A mononuclear copper complex with fluorescent properties, characterized in that: the molecular formula is C61H47CuClN3O2P2The crystal of the complex belongs to a triclinic crystal system, and the unit cell parameters are as follows: a = 12.73 a, b =18.42 a, c = 23.22 a, α = 79.21 °, β = 87.78 °, γ = 86.12 °; each complex molecule contains a copper ion, a benzimidazole phosphine ligand and a triphenylphosphine auxiliary ligand;
the structural formula of the benzimidazole phosphine ligand is as follows:
Figure 402168DEST_PATH_IMAGE001
the structural formula of the mononuclear copper complex is as follows:
Figure 755789DEST_PATH_IMAGE002
the mononuclear copper complex is used as an optical material; the preparation method specifically comprises the following steps:
(1) adding 2-3 mmol of cuprous chloride, 2-3 mmol of benzimidazolephosphine ligand and 2-3 mmol of triphenylphosphine into 20-25 ml of mixed solution of dichloromethane and acetonitrile, heating the mixture to 40-50 ℃, and continuously stirring and keeping for 2-3 hours at the temperature; wherein the mass ratio of cuprous chloride to the benzimidazole phosphine ligand and the triphenylphosphine is 1:1:1, and the volume ratio of dichloromethane to acetonitrile is 4: 1;
(2) and (2) filtering the solution reacted in the step (1), transferring the solution into a 30ml glass bottle, naturally volatilizing for 72-96 hours to obtain a complex crystal, filtering the crystal, washing with acetonitrile, and drying in vacuum to obtain the final product, namely the mononuclear copper complex.
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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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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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"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";张斌;《中国博士学位论文全文数据库 工程科技I辑》;20141215;第B014-51页 *

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