CN114106345A - Luminous copper-thiol polymer single crystal and preparation method thereof - Google Patents

Luminous copper-thiol polymer single crystal and preparation method thereof Download PDF

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CN114106345A
CN114106345A CN202111213169.1A CN202111213169A CN114106345A CN 114106345 A CN114106345 A CN 114106345A CN 202111213169 A CN202111213169 A CN 202111213169A CN 114106345 A CN114106345 A CN 114106345A
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copper
thiol
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CN114106345B (en
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姚传好
向慧鑫
黄维
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Ningbo Research Institute of Northwestern Polytechnical University
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Abstract

The invention provides a luminous copper-thiol polymer monocrystal, wherein the copper-thiol polymer is a Cu chain polymer protected by an adamantane thiol ligand, each basic unit comprises 4 Cu atoms and 4 adamantane thiol ligands, the Cu atoms and sulfur atoms in the adamantane thiol ligands are alternately connected to form a one-dimensional chain structure, and the chemical formula of the polymer is [ -Cu4(SC10H15)4‑]n. One of the purposes of the invention is to provide a luminescent copper-thiol polymer single crystal synthesized by ion induction, which has a unique chain structure compared with the reported copper nanoparticles and shows good photoluminescence performance in air. The invention also aims to provide a preparation method of the luminescent copper-thiol polymer single crystal.

Description

Luminous copper-thiol polymer single crystal and preparation method thereof
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a luminescent copper-thiol polymer single crystal and a preparation method thereof.
Background
In recent years, metal nanoparticles have attracted attention of a great number of scientific researchers due to their unique physicochemical properties. Among them, photoluminescence is one of its important characteristics. Research results show that photoluminescence of the metal nanoparticles has the following characteristics: good optical stability and biocompatibility, low toxicity, large Stokes shift and near-infrared luminescence. These characteristics make the fluorescent metal nanoparticles have good application prospects in the fields of biological imaging, biological probes, optical devices and the like. Therefore, the preparation of metal nanoparticles having photoluminescence properties is one of the hot spots pursued by the present nanocologists.
In the prior art, most of fluorescent metal nanoparticles are gold and silver noble metal particles, so that the cost is high, and the fluorescent metal nanoparticles are not suitable for large-scale popularization and application. The copper nanoparticles have the fluorescence property which is comparable to that of gold and silver noble metal nanoparticles, have the advantages of rich raw material reserves, economic preparation and the like, and have wide application prospects. Therefore, the copper nanoparticles have unique advantages in developing new cheap high-performance luminescent materials, and further development of the copper nanoparticles as the luminescent materials has extremely important scientific research value and economic value.
Disclosure of Invention
One of the purposes of the invention is to provide a luminescent copper-thiol polymer single crystal synthesized by ion induction, which has a unique chain structure compared with the reported copper nanoparticles and shows good photoluminescence performance in air.
The invention provides a luminous copper-thiol polymer monocrystal, wherein the luminous copper-thiol polymer is a Cu chain polymer protected by an adamantane thiol ligand, each basic unit comprises 4 Cu atoms and 4 adamantane thiol ligands, the Cu atoms and sulfur atoms in the adamantane thiol ligands are alternately connected to form a one-dimensional chain structure, and the chemical formula of the polymer is [ -Cu4(SC10H15)4-]n。
Optionally, the copper-thiol polymer has a chemical formula of [ -Cu ]4(SC10H15)4-]nBelonging to the monoclinic system, space group is C2/C.
Optionally, the copper-thiol polymer has crystallographic parameters of:
Figure BDA0003309602410000021
Figure BDA0003309602410000022
α＝90°，β＝117.093(3)，γ＝90°。
the invention also aims to provide a preparation method of the luminescent copper-thiol polymer single crystal.
In order to solve the above problems, the present invention provides a method for preparing a luminescent copper-thiol polymer single crystal, comprising the steps of:
s1, adding a metal induced ion solution into the TOAB solution, and uniformly stirring to obtain a white solution A;
s2, adding adamantane thiol into the white solution A in the step S1, adding a mixture of a copper salt solution and triphenylphosphine after the solution becomes colorless, and continuously stirring for reaction to obtain a milky white solution B;
s3 adding NaBH into the milky white solution B obtained in the step S24Reducing the complex of copper, and continuously stirring for reaction to obtain a black solution C;
s4, drying the black solution C obtained in the step S3 by using a rotary evaporator, extracting the obtained solid, and performing single crystal culture to obtain the finished product.
Alternatively, the inducing ion in step S1 is silver ion, and the silver salt added is silver nitrate, silver nitrite, silver chloride or silver acetate.
Optionally, the molar ratio of the added TOAB to the silver ions in the step S1 is (1-2): 1.
optionally, the molar ratio of the added adamantane thiol to the silver ions in the step S2 is (4-10): 1.
optionally, the copper salt in the step S2 is copper nitrate or copper chloride, and the molar ratio of the added copper ions to the silver ions is (1-2): 1.
alternatively, NaBH described in step S24The molar ratio of the copper ions to the copper ions is (5-15): 1.
alternatively, the solvent of the TOAB solution in step S1 is toluene or dichloromethane, and the solvent of the metal-induced ion solution is methanol, ethanol, or acetonitrile.
Compared with the prior art, the invention has the following advantages:
the S1 luminous copper-thiol polymer single crystal has higher fluorescence luminous performance in air atmosphere at room temperature. Can be designed to be used in the practical application fields of LED, high-resolution fluorescent probe, anti-counterfeiting and the like.
S2 the existing ultra-small copper nanoparticles are easy to suffer from air oxidation and difficult to exist stably. In this application, by ionic induction with NaBH4Reducing the thiol complex of copper to synthesize a copper-thiol polymer, the adamantane thiol ligand can protect the ultra-small copper nanoparticles from atmospheric oxidation.
S3 the method is a novel preparation method of the copper nano polymer, and has the advantages of simple operation, rapid preparation, low cost and the like. The development of a novel synthesis method and the research and development of stable and functionalized ultra-small copper nano materials can greatly promote the wide application of the copper-based nano materials in related fields, such as biology, photoelectricity and the like.
S4 compared with the copper nano-particles reported at present, the copper-thiol polymer has a unique chain structure.
Drawings
FIG. 1 is a schematic representation of the copper-sulfur framework structure of a luminescent copper-thiol polymer;
FIG. 2 is a schematic view of a chain structure of a luminescent copper-thiol polymer;
FIG. 3 is a graph showing the effect of a luminescent copper-thiol polymer single crystal under visible light and ultraviolet light.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
The invention is based on the idea of reacting NaBH by means of ion induction4Reducing a thiol complex of a copper salt to synthesize a copper-thiol polymer.
Example 1:
s1 10ml of toluene and 40mg of TOAB were put into a 50ml flask, and after dissolving by stirring, 10mg of silver acetate dissolved in 5ml of acetonitrile was added and stirred at 600rpm at room temperature for 30 min.
S2 adamantanethiol 50mg was added to the reaction solution in S1 and dissolved in 5mL acetonitrile10mg of CuCl2A mixture of 10mg of triphenylphosphine was added to the solution. The reaction was stirred at 600rpm for 1 hour.
After S31 hours, 40mg of NaBH4Dissolved in 5mL of ice water, the reaction solution in S2 was added to reduce the metal ions. The reaction was carried out at room temperature for 12 h.
And (3) evaporating the solvent of the reaction product in the S3 by using a rotary evaporator, extracting by using n-hexane, centrifuging, and volatilizing and crystallizing the supernatant to obtain the yellow transparent long-strip single crystal within 3-5 days.
Example 2:
S1A 50ml flask was charged with 10ml of methylene chloride and 40mg of TOAB, and after stirring and dissolving, 10mg of silver acetate dissolved in 5ml of ethanol was added and stirred at 600rpm at room temperature for 10 min.
S2 Add 50mg of adamantanethiol to the reaction solution in S1 and 10mg of CuCl dissolved in 5mL of ethanol2A mixture of 10mg of triphenylphosphine was added to the solution. The reaction was stirred at 600rpm for 1 hour.
After S31 hours, 40mg of NaBH4Dissolved in 5mL of ice water, the reaction solution in S2 was added to reduce the metal ions. The reaction was carried out at room temperature for 12 h.
S4, evaporating the solvent of the reaction product in the S3 by using a rotary evaporator, extracting by using n-hexane, centrifuging, and performing volatilization crystallization on the supernatant to obtain a yellow and transparent long-strip-shaped single crystal within 3-5 days.
Example 3:
s1 10ml toluene and 40mg TOAB were added to a 50ml flask, and after dissolution by stirring, 10mg silver nitrate dissolved in 5ml deionized water was added and stirred at 600rpm for 30min at room temperature to remove the aqueous phase.
S2 Add 50mg of adamantanethiol to the reaction solution in S1 and dissolve 10mg of CuCl in 5mL of methanol2A mixture of 10mg of triphenylphosphine was added to the solution. The reaction was stirred at 600rpm for 1 hour.
After S31 hours, 50mg of NaBH4Dissolved in 5mL of ice water, the reaction solution in S2 was added to reduce the metal ions. The reaction was carried out at room temperature for 12 h.
S4, evaporating the solvent of the reaction product in the S3 by using a rotary evaporator, extracting by using n-hexane, centrifuging, and performing volatilization crystallization on the supernatant to obtain a yellow and transparent long-strip-shaped single crystal within 3-5 days.
Example 4:
s1 10ml toluene and 40mg TOAB were added to a 50ml flask, and after dissolution by stirring, 10mg silver nitrate dissolved in 5ml deionized water was added and stirred at 600rpm for 30min at room temperature to remove the aqueous phase.
S2 Add 50mg of adamantanethiol to the reaction solution in S1 and 10mg of CuCl dissolved in 5mL of acetonitrile2A mixture of 10mg of triphenylphosphine was added to the solution. The reaction was stirred at 600rpm for 1 hour.
After S31 hours, 40mg of NaBH4Dissolved in 5mL of ice water, the reaction solution in S2 was added to reduce the metal ions. The reaction was carried out at room temperature for 12 h.
S4, evaporating the solvent of the reaction product in S3 by using a rotary evaporator, extracting by using n-hexane, centrifuging, dissolving the precipitate by adding dichloromethane, and volatilizing and crystallizing to obtain a yellow and transparent long-strip single crystal within 3-5 days.
The crystal structures of the novel Cu — S polymers prepared in example 1, example 2, example 3, and example 4 are shown in fig. 2. As can be seen from fig. 2, the ion-induced synthesized copper-thiol polymer is an adamantane thiol ligand protected Cu chain polymer. As shown in fig. 1, each base unit includes 4 Cu atoms and 4 adamantane thiol ligands, and the Cu atoms and the sulfur atoms in the adamantane thiol ligands are alternately connected to form a one-dimensional chain structure.
Referring to fig. 3, fig. 3 is a graph showing the effect of the copper-thiol polymer obtained in example 1 under visible light and ultraviolet light irradiation in an air atmosphere at room temperature, which illustrates that the copper-thiol polymer shows good photoluminescence performance in air.
Detailed crystal data are given in Table 1 below
TABLE 1 crystallographic parameters
Figure BDA0003309602410000061
Figure BDA0003309602410000071
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.

Claims (10)

1. A luminescent copper-thiol polymer single crystal, characterized by: the copper-thiol polymer is a Cu chain polymer protected by an adamantane thiol ligand, each basic unit comprises 4 Cu atoms and 4 adamantane thiol ligands, the Cu atoms and sulfur atoms in the adamantane thiol ligands are alternately connected to form a one-dimensional chain structure, and the chemical formula of the polymer is [ -Cu4(SC10H15)4-]n。
2. A luminescent copper-thiol polymer monocrystal according to claim 1, wherein: the copper-thiol polymer has a chemical formula of [ -Cu [ ]4(SC10H15)4-]nBelonging to the monoclinic system, space group is C2/C.
3. A luminescent copper-thiol polymer monocrystal according to claim 2, wherein the crystallographic parameters of the copper-thiol polymer are:
Figure FDA0003309602400000011
Figure FDA0003309602400000012
α＝90°，β＝117.093(3)，γ＝90°。
4. a method for preparing a luminescent copper-thiol polymer single crystal according to claim 1, comprising the steps of:
s1, adding a metal induced ion solution into the TOAB solution, and uniformly stirring to obtain a white solution A;
s2, adding adamantane thiol into the white solution A in the step S1, adding a mixture of a copper salt solution and triphenylphosphine after the solution becomes colorless, and continuously stirring for reaction to obtain a milky white solution B;
s3, adding NaBH into the milky white solution B obtained in the step S24Reducing the complex of copper, and continuously stirring for reaction to obtain a black solution C;
and S4, drying the black solution C obtained in the step S3 by using a rotary evaporator, extracting the obtained solid, and performing single crystal culture to obtain a finished product.
5. The method for producing a luminescent copper-thiol polymer single crystal according to claim 4, characterized in that: the inducing ions in the step S1 are silver ions, and the added silver salt is silver nitrate, silver nitrite, silver chloride or silver acetate.
6. The method for producing a luminescent copper-thiol polymer single crystal according to claim 5, wherein: the molar ratio of the added TOAB to the silver ions in the step S1 is (1-2): 1.
7. the method for producing a luminescent copper-thiol polymer single crystal according to claim 5, wherein: the molar ratio of the added adamantane thiol to the silver ions in the step S2 is (4-10): 1.
8. the method for producing a luminescent copper-thiol polymer single crystal according to claim 5, wherein: the copper salt in the step S2 is copper nitrate or copper chloride, and the molar ratio of the added copper ions to the silver ions is (1-2): 1.
9. the method for producing a luminescent copper-thiol polymer single crystal according to claim 8, characterized in that: NaBH described in step S24The molar ratio of the copper ions to the copper ions is (5-15): 1.
10. the method for producing a luminescent copper-thiol polymer single crystal according to claim 5, wherein: the solvent of the TOAB solution in step S1 is toluene or dichloromethane, and the solvent of the metal-induced ion solution is methanol, ethanol, or acetonitrile.
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