CN110129024B - Eight-core alkyne silver cluster material with thermochromic luminescence property and preparation method and application thereof - Google Patents

Eight-core alkyne silver cluster material with thermochromic luminescence property and preparation method and application thereof Download PDF

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CN110129024B
CN110129024B CN201910437358.3A CN201910437358A CN110129024B CN 110129024 B CN110129024 B CN 110129024B CN 201910437358 A CN201910437358 A CN 201910437358A CN 110129024 B CN110129024 B CN 110129024B
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alkyne
silver
thermochromic
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周坤
史飓峰
季久玉
陈志进
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Liaoning Shihua University
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    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
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    • G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
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    • G01K11/16—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance of organic materials
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    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
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    • G01K11/20—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials

Abstract

The invention discloses an eight-core silver alkyne cluster material with thermochromic luminescence property, which has the chemical formula as follows: c38H48Ag8F9NO6The structural chemical formula is as follows: ag8(ButC≡C)5(CF3COO)3(CH3CN), the eight-core alkyne silver cluster material is a silver cluster material with a novel structure, and the silver cluster material adopts tert-butyl alkyne silver ligand and CH3The CN ligand synthesized has excellent thermochromic luminescence property, and can be applied to the technical field of temperature sensing and detection.

Description

Eight-core alkyne silver cluster material with thermochromic luminescence property and preparation method and application thereof
Technical Field
The invention relates to the technical field of inorganic nano material synthesis, in particular to an eight-core alkyne silver cluster material with thermochromic luminescence property and a preparation method and application thereof.
Background
The formation of high-nuclear silver clusters is a complex process involving multiple component parts. Therefore, it is very challenging to construct metallic silver clusters in an ordered manner, i.e., the synthesis reaction of highly nuclear silver clusters is not controllable. However, many researchers still desire to be able to construct high nuclear silver clusters by incorporating the outstanding coordination characteristics of silver ions in combination with the unique properties of organic/inorganic ligands. At present, it contains C.ident.CR and SR (R ═ C ≡ CRtBu,tBuPh, etc.) functional groups have been frequently found.
However, a strategy for constructing a highly nuclear silver cluster having a special function has been sought. If a targeting group can be introduced during cluster formation, it is possible to produce predictable clusters. The material has a luminescent property sensitive to temperature, so that the material has potential application value in the field of biomedicine.
Therefore, it is one of the research directions whether the nuclear silver cluster compound with temperature-sensitive luminescent property and high luminescence property can be synthesized by introducing a guide group.
Disclosure of Invention
In view of the above, the invention discloses an octanuclear alkyne silver cluster material with thermochromic luminescence property, and a preparation method and application thereof, so as to provide a silver cluster material with a novel structure and functions.
In one aspect, the invention provides an eight-core silver alkyne cluster material with thermochromic luminescence property, and the chemical formula of the eight-core silver alkyne cluster material is as follows: c38H48Ag8F9NO6The structural chemical formula is Ag8(ButC≡C)5(CF3COO)3(CH3CN)。
Preferably, the eight-core alkyne silver cluster material belongs to a triclinic crystal system, the space group is P-1, and the unit cell parameter is
Figure BDA0002070923940000011
Figure BDA0002070923940000012
α＝101.9000(10)°，β＝92.7640(10)°，γ＝115.5780(10)°，
Figure BDA0002070923940000013
On the other hand, the invention also provides a preparation method of the eight-core alkyne silver cluster material with the thermochromic luminescence property, which specifically comprises the following steps:
weighing [ AgC ≡ C ] in sequencetBu]nAnd CF3COOAg is added into a reaction kettle, and CH which is also used as an organic ligand and a solvent is added3CN；
After the reactants in the reaction kettle are dissolved, reacting at the temperature of 70 ℃, and standing at room temperature after the reaction is finished to obtain yellow suspension;
and filtering the yellow turbid liquid to obtain colorless transparent filtrate, and volatilizing the colorless transparent filtrate to obtain colorless blocky crystals, namely the product.
Preferably, said [ AgC ≡ CtBu]nAnd CF3The molar ratio of COOAg is 1: 1.
more preferably, the yellow suspension is weakly acidic.
More preferably, the yellow suspension has a pH of 5.9.
Further preferably, the reaction kettle is placed in an ultrasonic cleaning machine for dissolving the reactants.
Further preferably, the volatilization temperature of the colorless transparent liquid is room temperature.
In addition, the invention also provides application of the eight-core alkyne silver cluster material with the thermochromic luminescence property to sensing and detecting temperature.
The invention provides an octanuclear alkyne silver cluster material with thermochromic luminescence property, which is a silver cluster material with a novel structure, and the silver cluster material adopts tert-butyl alkyne silver ligand and CH3The CN ligand synthesized has excellent thermochromic luminescence property, and can be applied to the technical field of temperature sensing and detection.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a crystal structure diagram of an octanuclear silver alkyne cluster material with thermochromic luminescence property provided by the disclosed embodiment of the invention;
FIG. 2 shows a solid-state emission spectrum of an octanuclear silver alkyne cluster material with thermochromic luminescence property, wherein the excitation wavelength is 396nm (298K), and the excitation wavelength is 478nm (77K);
fig. 3 is a linear graph of emission intensity and temperature of an octanuclear silver alkyne cluster material with thermochromic luminescence properties provided by the disclosed embodiment of the invention.
Detailed Description
The invention is explained in more detail below with reference to specific embodiments, which are not intended to limit the scope of the invention.
The embodiment provides an eight-core silver alkyne cluster material with thermochromic luminescence property, and the chemical formula of the eight-core silver alkyne cluster material is as follows: c38H48Ag8F9NO6The structural chemical formula is Ag8(ButC≡C)5(CF3COO)3(CH3CN), the octanuclear alkyne silver cluster material belongs to a triclinic crystal system, the space group is P-1, and the unit cell parameter is
Figure BDA0002070923940000031
Figure BDA0002070923940000032
α＝101.9000(10)°，β＝92.7640(10)°，γ＝115.5780(10)°，
Figure BDA0002070923940000033
The preparation method of the eight-core alkyne silver cluster material with the thermochromic luminescence property comprises the following specific steps:
weighing [ AgC.ident.C ] successively using an analytical balancetBu]nAnd CF3COOAg is added into the reaction kettle, and CH is added3CN serves as both a solvent and an organic ligand, wherein,tbu means tert-butyl;
after the reactants in the reaction kettle are dissolved, putting the reaction kettle into an oven at the temperature of 70 ℃ for reaction for 24 hours, and then standing the reaction kettle at room temperature to obtain yellow suspension;
filtering the yellow suspension through filter paper to obtain colorless transparent filtrate, storing the filtrate in a beaker, slowly volatilizing at room temperature, and volatilizing for about two days to obtain colorless massive crystals, namely the product.
Wherein [ AgC ≡ CtBu]nAnd CF3The molar ratio of COOAg is 1: 1, for silver cluster materials, the key point is the proportion of reaction raw materials, and the inventor finds out through a large number of experiments in the research and development process that: only according to the above proportion, the silver cluster material with the crystal structure shown in fig. 1 can be synthesized.
The yellow suspension obtained by the reaction is weakly acidic, wherein silver mirror reaction is not easy to occur under the acidic condition, and Ag is facilitated+The pH of the yellow suspension is preferably 5.9, and the above colorless transparent liquid is volatilized at room temperature, usually 25 ℃. In the case of dissolving the reactants, the reaction vessel is preferably placed in an ultrasonic cleaning machine to accelerate the dissolution rate by ultrasonic waves, and the solvent is usually completed within 30 minutes.
Solid-state luminescence spectroscopy studies were conducted on the octanuclear silver alkyne cluster materials with thermochromic luminescent properties in the above embodiments. As can be seen from fig. 2: the material has good emission behavior at an excitation wavelength of 396nm and excellent emission intensity at normal temperature, and when the solid powder of the material is irradiated under an ultraviolet lamp (the excitation wavelength is 365nm), the material is found to emit weak purple light, and when the solid powder of the material is immersed in liquid nitrogen for a few seconds and then is irradiated under the ultraviolet lamp (the excitation wavelength is 365nm), the material is found to emit strong green light. While the green light will gradually disappear as the temperature gradually rises to 298K. However, when the temperature is changed between 298K and 77K, the thermochromic luminescence behavior is reversible, and therefore, the octaaryne silver cluster material with the thermochromic luminescence property can be used for sensing the temperature. Furthermore, as the temperature gradually decreases (from 298K to 77K), the emission intensity correspondingly increases, because: along with the reduction of the temperature, the rigidity of the material is enhanced, and the intersystem crossing between metal and metal is accelerated, so that the loss of non-radiative energy is reduced; mainly due to Ag · Ag interactions and the transfer of ligand to metal charge. At 298-173K, the maximum emission wavelength was 555nm, and as the temperature decreased from 130 to 77K, the maximum emission wavelength was slightly red-shifted to 570 nm.
The invention is further illustrated by the following specific examples.
Example 1: synthesis of thermochromic luminous octanuclear silver alkyne cluster material
Will [ AgC ≡ CtBu]n(0.0566g,0.2994mmol) and CF3COOAg (0.0660g,0.2987mmol) was added to the reactor, and CH was added3CN is used as a solvent, then the mixture is put into an oven with the temperature of 70 ℃ for reaction for 24 hours, and the mixture is placed at room temperature to obtain yellow suspension, wherein the pH value of the yellow suspension is 5.9;
and filtering the yellow suspension by using filter paper to obtain colorless transparent liquid, storing the colorless transparent liquid in a beaker, slowly volatilizing at room temperature, and volatilizing for about two days to obtain colorless blocky crystals, namely the thermochromic luminous octanuclear silver alkyne cluster material.
Example 2: thermochromic phenomenon of thermochromic luminous octanuclear silver alkyne cluster material
A sample of the thermochromic luminous eight-core silver alkyne cluster material prepared in example 1 is taken and emits weak purple light at room temperature under the irradiation of an ultraviolet lamp. When the sample was immersed in liquid nitrogen, it emitted intense green light under the same ultraviolet lamp illumination. When the temperature of the sample gradually increased to room temperature, the purple color recovered. The above-mentioned macroscopic thermochromic luminescence behavior is reversible and can be applied to the sensing of temperature. The linear graph between the corresponding emission intensity and the temperature of the thermochromic luminous octanuclear silver alkyne cluster material is shown in figure 3.
Example 3: physical property detection of synthesized thermochromic luminous octanuclear silver alkyne cluster material
The thermochromic luminous eight-core silver alkyne cluster material prepared in example 1 is taken for further characterization, and the process is as follows:
(1) determination of Crystal Structure
X-ray single crystal diffraction data of the complexes were measured on a Bruker D8QUEST type diffractometer using single crystal samples of appropriate size. A graphite monochromator is used, Mo-K alpha (lambda is 0.071073nm) is used as a light source, and a Saint software package is used for data reduction. The structure is resolved by a SHELXL-2014 program, and a full-matrix least square method (fill-matrix least square-element based on F is adopted2) And (5) performing structure fine trimming.
The detailed crystal measurement data are shown in Table 1, the important bond length and bond angle data are shown in Table 2, the crystal structure diagram is shown in FIG. 1, and the temperature-variable fluorescence spectrum is shown in FIG. 2.
Table 1: principal crystallographic data of thermochromic luminescent silver cluster material
Figure BDA0002070923940000041
Figure BDA0002070923940000051
Table 2: important bond length
Figure BDA0002070923940000053
Angle of harmony key (°)
Figure BDA0002070923940000052
Figure BDA0002070923940000061
Key angle (°)
Figure BDA0002070923940000062
Remarking: symmetric code #1-x +1, -y +1, -z +2
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It is to be understood that the present invention is not limited to what has been described above, and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.

Claims (5)

1. A preparation method of an eight-core alkyne silver cluster material with thermochromic luminescence properties is characterized by comprising the following steps:
weighing [ AgC ≡ C ] in sequencetBu]nAnd CF3COOAg is added into a reaction kettle, and CH which is also used as an organic ligand and a solvent is added3CN；
After the reactants in the reaction kettle are dissolved, reacting at the temperature of 70 ℃, and standing at room temperature after the reaction is finished to obtain yellow suspension;
filtering the yellow suspension to obtain colorless transparent filtrate, and volatilizing the colorless transparent filtrate to obtain colorless blocky crystals, namely products;
the [ AgC ≡ CtBu]nAnd CF3The molar ratio of COOAg is 1: 1;
the pH of the yellow suspension was 5.9.
2. The preparation method of the octanuclear alkyne silver cluster material with thermochromic luminescence property as claimed in claim 1, wherein the reaction kettle is put into an ultrasonic cleaning machine for reactant dissolution.
3. The method for preparing the eight-core alkyne silver cluster material with the thermochromic luminescence property of claim 1, wherein the volatilization temperature of the colorless transparent liquid is room temperature.
4. An octanuclear silver alkyne cluster material with thermochromic luminescence properties, which is prepared by the method of any one of claims 1 to 3, and has the chemical formula: c38H48Ag8F9NO6The structural chemical formula is Ag8(ButC≡C)5(CF3COO)3(CH3CN)；
The eight-core alkyne silver cluster material belongs to a triclinic crystal system, the space group is P-1, and the unit cell parameter is
Figure FDA0003126333810000011
Figure FDA0003126333810000012
α＝101.9000(10)°，β＝92.7640(10)°，γ＝115.5780(10)°，
Figure FDA0003126333810000013
5. Use of the octanuclear silver alkyne cluster material with thermochromic luminescence property of claim 4 for sensing and detecting temperature.
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CN111943964B (en) * 2020-08-26 2022-09-13 辽宁石油化工大学 Twenty-eight-core silver alkyne cluster material constructed by taking molybdic polyacid as anion template and preparation method thereof
CN111848700B (en) * 2020-08-26 2022-09-30 辽宁石油化工大学 Twenty-four-core alkyne silver cluster material constructed by taking vanadium polyacid as anion template and preparation method thereof

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CN109776580A (en) * 2019-03-20 2019-05-21 辽宁石油化工大学 Silver-colored clustered materials and its preparation method and application with thermo-color luminosity

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Kun Zhou et al..Facile assembly of 1D multinuclear Agn(n=11, 11, 12) alkynyl chains with CF3COO-/CH3COO- as the auxiliary ligand.《RSC Adv.》.2014,第4卷 *

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