CN111548368A - Copper nanocluster with high stability and near-infrared phosphorescence and preparation method thereof - Google Patents
Copper nanocluster with high stability and near-infrared phosphorescence and preparation method thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 73
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 23
- 229960001701 chloroform Drugs 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- GNXBFFHXJDZGEK-UHFFFAOYSA-N 4-tert-butylbenzenethiol Chemical compound CC(C)(C)C1=CC=C(S)C=C1 GNXBFFHXJDZGEK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- -1 sodium hexafluoroantimonate Chemical compound 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims description 3
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000002390 rotary evaporation Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000012298 atmosphere Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000006862 quantum yield reaction Methods 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- UIBGMVGOKJXTGD-UHFFFAOYSA-N C1(=CC=CC=C1)S.C(C)(C)(C)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)S.C(C)(C)(C)C1=CC=CC=C1 UIBGMVGOKJXTGD-UHFFFAOYSA-N 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 238000005424 photoluminescence Methods 0.000 description 4
- 230000006399 behavior Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000000090 biomarker Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YWBHROUQJYHSOR-UHFFFAOYSA-N $l^{1}-selanylbenzene Chemical compound [Se]C1=CC=CC=C1 YWBHROUQJYHSOR-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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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 Table
- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a copper nanocluster with high stability and near-infrared phosphorescence and a preparation method thereof, belonging to the cross field of coordination chemistry and nano materials. The copper nanocluster takes common p-tert-butylbenzene thiophenol and triphenylphosphine as protection ligands, and a copper nanocluster material with high yield and near-infrared luminescence is synthesized by a simple one-pot method at room temperature in an air atmosphere. The molecular formula of the copper nanocluster is [ Cu ]11(SC10H13)9(PC18H15)6](SbF6)2Belongs to the monoclinic system, and the space group is P21/n. At room temperature, the solution and the solid of the copper nanocluster have strong red phosphorescence, and the absolute quantum yield of the solid is 22%. The solution of the copper nanocluster has strong stability at room temperature in an air atmosphere.
Description
Technical Field
The invention belongs to the subject of nano materials, and relates to a copper nanocluster with high stability and near-infrared phosphorescence and a preparation method thereof.
Background
For having d10Nanoclusters of electronic metals, photo-inducedLuminescence is one of the most interesting properties. Among them, cu (i) clusters have been widely studied because of their abundant raw material reserves, low prices, and ready availability, and particularly, their unique optical properties, and they have been used in high-efficiency light-emitting inks, organic light-emitting materials, and the like.
Some Cu-X (X represents a halogen atom, e.g. Cu)4I4、Cu3I6Etc.) clusters generally have strong phosphorescent and thermochromic behavior in the solid state. In order to pursue more copper nanoclusters having novel structural and optical properties, scientists used some organic ligands to synthesize the copper nanoclusters, such as thiol/selenium ligands, phosphine ligands, alkyne ligands, etc. Shimada and his colleagues reported a series of Cu (I) clusters-Cu protected by thiol-phosphine bridging ligands2、Cu4And Cu6And found to have different light emission behaviors. The subject group of professor Zhuman utilizes ligand effect and obtains two copper nanoclusters-Cu by using the same synthesis method13And Cu8They are protected by phenylselenol and thiophenol, respectively. The results show that the difference of the ligands induces the structural difference, thereby leading to different thermochromic behaviors.
However, most of the atom-accurate copper nanoclusters reported so far only report their luminescence properties in a solid state, and few mention is made of the optical properties of the copper nanoclusters in a solution state. This may be due to the lack of "gold-philic" interactions and instability of the copper nanoclusters in the solution state. This phenomenon has greatly hindered the use of copper nanoclusters in photosensitive materials, cell imaging, and biomarkers, among others. Therefore, the copper nanoclusters with good stability and strong fluorescence under the condition of preparing the solution still have the difficult problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a copper nanocluster with high stability and near-infrared phosphorescence and a preparation method thereof. The copper nanocluster of the invention has good stability and photoluminescence performance, and particularly has high stability, near-infrared phosphorescence and larger Stokes shift in a solution state, so that the copper nanocluster has potential application value in the fields of biological markers and the like.
The copper nanocluster is protected by a mixed ligand and has the following molecular formula: [ Cu ]11(SC10H13)9(PC18H15)6](SbF6)2Abbreviated as Cu11Belongs to the monoclinic system, the space group is P21/n,
the preparation method of the copper nanocluster comprises the following steps:
the whole preparation process is carried out at room temperature under the condition of uniform stirring at 1200 rpm. First, 40 mg of cuprous chloride, 100 mg of tetraoctylammonium bromide, 15 ml of chloroform and 10 ml of methanol were added to a 100 ml pear-shaped flask. After 15 minutes of reaction, 100 mg of triphenylphosphine were added; after reacting for 30 minutes, adding 70 microliter of 4-tert-butyl thiophenol into the reaction system; after 30 minutes, weighing 50 mg of sodium borohydride solid, adding 5 ml of deionized water to prepare a solution, and directly and quickly adding the solution into the pear-shaped flask, wherein the solution immediately turns black; after the reaction is continuously stirred for 24 hours, stirring magnetons and aqueous solution in the reaction system are removed, and 5 ml of methanol solution dissolved with 100 mg of sodium hexafluoroantimonate is added; and then removing the organic solvent by a rotary evaporator, washing the organic solvent by methanol and toluene for several times respectively to remove redundant ligand and byproducts, finally dissolving the product in trichloromethane, diffusing normal hexane into the trichloromethane solution by using a gas phase diffusion method, and obtaining yellow needle-shaped crystals after one week, namely the target product.
By means of an X-ray single crystal diffractometer, we obtained Cu11The structure of the nanoclusters. The results showed that the copper nanoclusters contained 11 Cu atoms, 9 4-tert-butylphenol ligands, and 6 triphenylphosphine ligands (fig. 1), allPerCu-P and mu3The coordination of-S-Cu forms a cage structure (FIG. 2). In addition, two sbfs were found at the periphery of the copper nanocluster molecule6 -Counter ion (fig. 1). In conclusion, the molecular formula of the copper nanocluster is determined as [ Cu ]11(SC10H13)9(PC18H15)6](SbF6)2。
For Cu11The uv-vis absorption spectra in the nanocluster solution were measured. Mixing Cu11The crystal was dissolved in chloroform, and its UV-visible absorption spectrum showed a shoulder only at 400nm, as shown in FIG. 3.
Method for Cu in solution state by using ultraviolet-visible light absorption spectrum11The stability of the nanoclusters was verified and the results are shown in fig. 4. Mixing Cu11The nanoclusters are dissolved in trichloromethane, and after the sample is placed in the air atmosphere at room temperature for 2 months, the ultraviolet-visible light absorption spectrum of the sample has no obvious change, which proves that Cu11The cluster has better stability in the solution.
Cu11Nanoclusters exhibit near infrared photoluminescence in both solids and solutions. FIG. 5 shows Cu11Photos of the solid of the nanocluster and the chloroform solution under the irradiation of a 365nm ultraviolet lamp have visible bright red light; FIG. 6 shows Cu11Excitation and emission spectra of nanoclusters in solids and solutions. Cu11Maximum emission wavelength (. lamda.) in chloroform solutionem) Is 685nm (excitation wavelength is lambda)ex430nm) and the maximum emission wavelength of the solid (λ)em) At 675nm (excitation wavelength. lambda.ex450 nm). Compared with the ultraviolet absorption spectrum, the Stokes shift is 280 nm. By using integrating sphere to Cu11The quantum yield of the nanoclusters was measured, and the results showed Cu11The absolute quantum yields of nanoclusters in chloroform solution and solid were 7% and 22%, respectively.
The invention uses direct synthesis method to obtain a copper nanocluster with novel and stable structure and photoluminescence property. The copper nanocluster shows good stability and photoluminescence performance in solid and solution, and has potential application value in the fields of biological labeling and the like. The synthesis method of the cluster is simple and convenient, and the precise structure of the cluster can be represented by an X-ray single crystal diffractometer.
Drawings
FIG. 1 shows the present invention [ Cu ]11(SC10H13)9(PC18H15)6](SbF6)2Schematic diagram of the general structure of (1).
FIG. 2 is Cu11The overall framework of cluster structure.
FIG. 3 is Cu11Ultraviolet-visible absorption spectrum of the cluster.
FIG. 4 is Cu11Stability test data for clusters.
FIG. 5 is Cu11Photographs of the solid state and the solution state under a fluorescent lamp and a 365nm ultraviolet lamp.
FIG. 6 is Cu11Excitation, emission spectra in solid and solution state.
Detailed Description
The invention is further illustrated by the following specific examples:
example 1: synthesis of copper nanoclusters
The whole preparation process is carried out at room temperature under the condition of uniform stirring at 1200 rpm. Firstly, 40 mg of cuprous chloride, 100 mg of tetraoctylammonium bromide, 15 ml of trichloromethane and 10 ml of methanol are added into a 100 ml pear-shaped flask, and after 15 minutes of reaction, 100 mg of triphenylphosphine is added; after reacting for 30 minutes, adding 70 microliter of 4-tert-butyl thiophenol into the reaction system; after continuing to react for 30 minutes, quickly adding 5 ml of deionized water solution in which 50 mg of sodium borohydride is dissolved into the pear-shaped flask, and immediately turning the color of the solution black; continuously stirring the reaction for 24 hours, then removing the stirring magnetons and the aqueous solution in the reaction system, adding 5 ml of methanol solution dissolved with 100 mg of sodium hexafluoroantimonate, and removing the organic solvent through a rotary evaporator; and then, washing the product for multiple times by using methanol and toluene respectively to remove redundant ligand and byproducts, finally dissolving the product in chloroform, diffusing n-hexane into the chloroform solution by using a gas phase diffusion method, and obtaining yellow needle crystals after one week, namely the target product.
Example 2: characterization of the Crystal Structure
The copper nanoclusters produced in example 1 were further characterized as follows:
(1) determination of Crystal Structure
Selecting needle-shaped crystals under optical microscope, selecting one crystal with good quality and large size under nitrogen atmosphere (170K), and preparing with Ga-K αThe Bruker D8 Venture diffractometer from the light source collected the data, which were then integrated and restored using APEX 3 software. The structure was then parsed and refined in Olex 2 software using ShelXT and ShelXL programs. All Au, Ag and S atoms are directly found, and the remaining non-hydrogen atoms are generated by differential fourier synthesis. All non-hydrogen atoms are anisotropically refined. All hydrogen atoms are given positions by geometric calculations and are isotropically refined. The electron density generated by residual solvent molecules was filtered from the data using the SQUEEZE method in PLATON. Detailed crystal data are shown in table 1 below, and important bond length data are shown in table 2 below.
TABLE 1 Cu11Cluster principal crystallographic data
TABLE 2 Cu11Nanocluster dominant bond length statistics
Cu1-Cu2 | 2.783(4) | Cu9-S3 | 2.239(6) |
Cu1-Cu6 | 2.995(4) | Cu6-S4 | 2.238(5) |
Cu2-Cu11 | 3.039(4) | Cu8-S4 | 2.277(5) |
Cu6-Cu11 | 3.045(4) | Cu11-S4 | 2.248(5) |
Cu7-Cu11 | 2.894(4) | Cu1-S5 | 2.274(5) |
Cu5-P1 | 2.223(5) | Cu3-S5 | 2.260(5) |
Cu10-P2 | 2.242(6) | Cu7-S5 | 2.234(5) |
Cu4-P3 | 2.203(5) | Cu3-S6 | 2.272(5) |
Cu9-P4 | 2.199(5) | Cu6-S6 | 2.293(5) |
Cu8-P5 | 2.212(5) | Cu10-S6 | 2.259(5) |
Cu3-P6 | 2.204(6) | Cu2-S7 | 2.283(5) |
Cu1-S1 | 2.220(5) | Cu5-S7 | 2.250(5) |
Cu5-S1 | 2.284(5) | Cu8-S7 | 2.243(5) |
Cu6-S1 | 2.264(5) | Cu2-S8 | 2.226(5) |
Cu1-S2 | 2.235(5) | Cu9-S8 | 2.249(5) |
Cu2-S2 | 2.288(5) | Cu11-S8 | 2.221(5) |
Cu4-S2 | 2.296(4) | Cu7-S9 | 2.215(6) |
Cu4-S3 | 2.247(5) | Cu10-S9 | 2.304(5) |
Cu7-S3 | 2.273(5) | Cu11-S9 | 2.239(6) |
The above examples are merely illustrative of the present invention, and other embodiments of the present invention are possible. However, all the technical solutions formed by equivalent alternatives or equivalent modifications fall within the protection scope of the present invention.
Claims (4)
2. the copper nanocluster according to claim 1, characterized in that:
the copper nanocluster consists of 11 Cu atoms, 9 4-tert-butyl thiophenol ligands and 6 triphenylphosphine ligands and consists of P-Cu and mu3-S-Cu coordinates to form a cage structure and is provided with two SbFs6 -A counter ion.
3. A method for producing the copper nanoclusters of claim 1 or 2, characterized by comprising the steps of:
adding 40 mg of cuprous chloride, 100 mg of tetraoctylammonium bromide, 15 ml of trichloromethane and 10 ml of methanol into a reactor, reacting for 15 minutes, and adding 100 mg of triphenylphosphine; after reacting for 30 minutes, adding 70 microliter of 4-tert-butyl thiophenol into the reaction system; after 30 minutes, weighing 50 mg of sodium borohydride solid, adding the sodium borohydride solid into deionized water to prepare a solution, and directly adding the solution into the system, wherein the solution immediately turns black; after the reaction is continuously stirred for 24 hours, stirring magnetons and aqueous solution in the reaction system are removed, and 5 ml of methanol solution dissolved with 100 mg of sodium hexafluoroantimonate is added; and then, removing the solvent by rotary evaporation, washing by using methanol and toluene respectively, dissolving the product in chloroform, diffusing n-hexane into the chloroform solution by using a gas phase diffusion method, and obtaining yellow needle-shaped crystals after one week, namely the target product.
4. The production method according to claim 3, characterized in that:
the whole preparation process is carried out at room temperature under the condition of uniform stirring at 1200 rpm.
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CN112110955A (en) * | 2020-09-28 | 2020-12-22 | 安徽医科大学 | AuCu with high phosphorescence quantum yield in air atmosphere14Nanocluster and method for preparing same |
CN113025316A (en) * | 2021-03-15 | 2021-06-25 | 山东大学 | High-quantum-yield copper nanocluster fluorescent nanoflower, preparation method thereof and application thereof in LED |
CN113278031A (en) * | 2021-05-21 | 2021-08-20 | 福州大学 | Copper-based nanocluster, ionic liquid induced synthesis method and application |
CN116063242A (en) * | 2023-02-07 | 2023-05-05 | 郑州大学 | Chiral Cu capable of emitting near infrared light 6 Cluster material and application thereof in night vision imaging |
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Cited By (7)
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CN112110955A (en) * | 2020-09-28 | 2020-12-22 | 安徽医科大学 | AuCu with high phosphorescence quantum yield in air atmosphere14Nanocluster and method for preparing same |
CN112110955B (en) * | 2020-09-28 | 2023-05-30 | 安徽医科大学 | Aucu with high phosphorescence quantum yield in air atmosphere 14 Nanoclusters and methods of making the same |
CN113025316A (en) * | 2021-03-15 | 2021-06-25 | 山东大学 | High-quantum-yield copper nanocluster fluorescent nanoflower, preparation method thereof and application thereof in LED |
US12021165B2 (en) | 2021-03-15 | 2024-06-25 | Shan Dong University | Preparation process and LED application of copper nanoclusters fluorescent nanoflowers with high quantum yield |
CN113278031A (en) * | 2021-05-21 | 2021-08-20 | 福州大学 | Copper-based nanocluster, ionic liquid induced synthesis method and application |
CN116063242A (en) * | 2023-02-07 | 2023-05-05 | 郑州大学 | Chiral Cu capable of emitting near infrared light 6 Cluster material and application thereof in night vision imaging |
CN116063242B (en) * | 2023-02-07 | 2024-02-27 | 郑州大学 | Chiral Cu capable of emitting near infrared light 6 Cluster material and application thereof in night vision imaging |
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