CN112110955A - AuCu with high phosphorescence quantum yield in air atmosphere14Nanocluster and method for preparing same - Google Patents
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- 229910015371 AuCu Inorganic materials 0.000 title claims abstract description 24
- 238000006862 quantum yield reaction Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 9
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- LIYGDNBFEBKBBZ-UHFFFAOYSA-N 3-[2-cyanoethyl(phenyl)phosphanyl]propanenitrile Chemical compound N#CCCP(CCC#N)C1=CC=CC=C1 LIYGDNBFEBKBBZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- GNXBFFHXJDZGEK-UHFFFAOYSA-N 4-tert-butylbenzenethiol Chemical compound CC(C)(C)C1=CC=C(S)C=C1 GNXBFFHXJDZGEK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 229910052737 gold Inorganic materials 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000006227 byproduct Substances 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
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- -1 sodium hexafluoroantimonate Chemical compound 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
- 238000005303 weighing Methods 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims 2
- 239000000523 sample Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000005424 photoluminescence Methods 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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Abstract
The invention discloses AuCu with high phosphorescence quantum yield in air atmosphere14Nanoclusters and method of making thereof, wherein AuCu14The nanocluster is an AuCu alloy nanocluster protected by mixed ligands, and comprises 1 Au atom, 14 Cu atoms, 12 4-tert-butyl thiophenol ligands and 6 bis (2-cyanoethyl) phenylphosphine ligands, and the periphery of the nanocluster is provided with an SbF6 ‑A counterion; the AuCu14The precise structure of the nanocluster contains an Au atomic core and a metal cage consisting of 8 Cu (I) atoms. The cluster has higher phosphorescence luminous performance at room temperature in air atmosphere and relative quantum yieldThe ratio was 71.35%. The cluster is expected to be designed to be used in the practical application fields of LED, high-resolution fluorescent nano probe, anti-counterfeiting and the like in the future.
Description
Technical Field
The invention belongs to the subject of nano materials, and particularly relates to AuCu with high phosphorescence quantum yield in air atmosphere14Nanoclusters and methods of making the same.
Background
In recent years, thiol-containing ligand-protected metal nanoclusters have received attention from a wide variety 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 nanoclusters has the following characteristics: good optical stability, good biocompatibility, low toxicity, large Stokes shift and near infrared luminescence. The characteristics enable the fluorescent metal nanocluster to have good application prospects in the fields of biological imaging, biological probes, optical devices and the like. Therefore, the preparation of metal nanoclusters having photoluminescence becomes one of hot spots pursued by current cluster materialists.
To date, tens of clusters with photoluminescence have been found. Based on the accurate structure of the luminescent material, the photoluminescence mechanism of the luminescent material is studied in detail by combining theoretical calculation, and a method for intensively and effectively improving the luminous efficiency is provided. Such as altering the electron donating ability of the surface ligand, incorporating a second metal, utilizing crystallization induction, and limiting maximum intramolecular movement by "aggregate settling," etc. The use of these methods to improve the light emitting efficiency of metal nanoclusters to some extent, such as Lee et al by utilizing the addition of excess TOA+Make Au22(GS)18The light-emitting efficiency is improved to 60% by transferring from the water phase to the toluene phase, however, Au22(GS)18@ TOA is a mixture, which limits its application to some extent. Furthermore, Wang et al succeeded in increasing the rod-like luminous efficiency from 0.2% to 40% by doping with Ag atoms. Nevertheless, the photoluminescence efficiency of metal nanoclusters with free valence electrons is still generally low (below 20%) at present. In addition, the emission lifetime of most of the luminescent metal nanoclusters reported before is usually in the nanosecond range, metal nanoclusters with phosphorescent properties are still rare, and the phosphorescent quantum yield of the metal nanoclusters at room temperature is still to be further improved, which is beneficial for the metal nanoclusters to become LED luminescent materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing a high-temperature air atmosphereAuCu with high phosphorescence quantum yield (71.3%) in enclosure14Nanoclusters and methods of making the same. AuCu of the invention14The nanoclusters exhibit good photoluminescent properties and give rise to their precise structure.
AuCu of the invention14The nanocluster is a mixed ligand protected AuCu alloy nanocluster, which comprises 1 Au atom, 14 Cu atoms, 12 4-tert-butyl thiophenol ligands and 6 bis (2-cyanoethyl) phenylphosphine ligands, and is peripherally provided with an SbF6 -A counterion; the precise structure of the AuCu nanocluster contains an Au atomic core and a metal cage consisting of 14 Cu (I) atoms.
The AuCu nanocluster has the following molecular formula:
[AuCu14(C10H13S)12(C12H13N2P)6](SbF6) Abbreviated as AuCu14Belongs to the triclinic system, the space group is P-1,
α＝83.358(7)°，β＝62.415(6)°，γ＝65.215(6)°，
the preparation method of the AuCu nanocluster comprises the following steps:
first, 400. mu.L of an aqueous solution of sodium tetrabromoaurate (0.1g/mL), 130mg of tetraoctylammonium bromide and 15mL of methylene chloride were placed in a 100mL pear-shaped flask, and after 30 minutes, 150. mu.L of 4-tert-butylphenol was added to the reaction system; after 60 minutes of reaction, 80mg of Cu (NO) was added3)2Dissolving in 5mL of methanol and adding into a reaction system; after 30 minutes of reaction, 150mg of bis (2-cyanoethyl) phenylphosphine were added; after 60 minutes, weighing 150mg of sodium borohydride solid, adding 5mL 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 was continued for 18 hours under stirring, the stirring magneton and the aqueous solution in the reaction system were removed, and 5mL of methanol containing 100mg of sodium hexafluoroantimonate dissolved therein was addedA solution; and then removing the organic solvent by a rotary evaporator, washing by using methanol and toluene respectively to remove redundant ligand and byproducts, finally dissolving the product in dichloromethane, diffusing n-hexane into dichloromethane solution by using a gas phase diffusion method, and obtaining red crystals after one week, namely the target product.
By means of an X-ray single crystal diffractometer, we obtained AuCu14The structure of the nanoclusters. The results show that the AuCu nanocluster includes 1 Au atom, 14 Cu atoms, 12 4-tert-butylphenol ligands, and 6 triphenylphosphine ligands (fig. 1). In addition, in AuCu14One SbF is found at the periphery of the nanocluster molecule6 -A counter ion. To sum up, the AuCu14The molecular formula of the nanocluster is determined as [ AuCu ]14(C10H13S)12(C12H13N2P)6](SbF6)。
Mixing AuCu14Dissolution of nanoclusters in dichloromethane: the methanol is 1: electrospray mass spectrometry was performed in solution at 1 (volume ratio). As a result, as shown in FIG. 2, a molecular ion peak was observed at a position where m/z was 4367.35Da, corresponding to a molecular formula of [ AuCu [ ]14(C10H13S)12(C12H13N2P)6]+. In addition, distinct molecular ion peaks were also observed at 4151.27Da, 3935.19Da and 3717.11Da, respectively corresponding to the molecular formula [ AuCu [ ]14(C10H13S)12(C12H13N2P)5]+、[AuCu14(C10H13S)12(C12H13N2P)4]+And [ AuCu ]14(C10H13S)12(C12H13N2P)3]+。
For AuCu14The uv-vis absorption spectra in the nanocluster dichloromethane solution were measured. Mixing AuCu14The crystal is dissolved in dichloromethane, and has ultraviolet-visible absorption spectra at 410nm, 455nm and 515nmThe distinct absorption peaks are shown in FIG. 3.
AuCu14The nanoclusters exhibit good photoluminescence properties. FIG. 4 shows AuCu14Fluorescence spectrum of nanoclusters. AuCu14Maximum emission wavelength (lambda) of nanoclusters in dichloromethane solutionem) Is 625nm (excitation wavelength is lambda)ex410nm), maximum emission wavelength in the solid state (λ)em) Is 630nm (excitation wavelength lambda)ex410nm) with a stokes shift of about 220 nm. By comparing with rhodamine B solution, AuCu is obtained14The relative quantum yield of the nanoclusters in dichloromethane was 71.3%. In addition, FIG. 5 shows AuCu14The fluorescence emission lifetime of the nanoclusters is 1.23 microseconds, the luminescence quenching can be promoted by introducing oxygen (fig. 6), and the fluorescence can be recovered even stronger than the original luminescence intensity by introducing nitrogen. These results indicate that it has phosphorescent emission behavior.
The invention uses direct synthesis method to obtain AuCu nanocluster [ AuCu ] with high quantum yield and phosphorescent light-emitting behavior14(C10H13S)12(C12H13N2P)6](SbF6). 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. Further, AuCu14The nanoclusters exhibit good phosphorescent properties.
Drawings
FIG. 1 is AuCu14Schematic of the structure of nanoclusters.
FIG. 2 is AuCu14Electrospray mass spectrum of nanoclusters.
FIG. 3 is AuCu14Uv-vis absorption spectrum of nanoclusters.
FIG. 4 is AuCu14Emission spectrum of nanoclusters.
FIG. 5 is AuCu14Luminescence lifetime curve of nanoclusters.
FIG. 6 is AuCu14Emission curve pair O of nanoclusters2The response map of (2).
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1: AuCu14Synthesis of nanoclusters
The whole preparation process is carried out at room temperature under the condition of uniform stirring at 1200 rpm. First, 400 μ l of an aqueous solution of sodium tetrabromoaurate (0.1g per ml), 130mg of tetraoctylammonium bromide and 15ml of methylene chloride were placed in a 100ml pear-shaped flask. After 30 minutes, 150 microliters of 4-tert-butyl thiophenol was added to the reaction system; after 60 minutes of reaction, 80mg of Cu (NO) was added3)2Dissolving in 5ml of methanol and adding into the solution; after 30 minutes of reaction, 150mg of bis (2-cyanoethyl) phenylphosphine were added; after 60 minutes, weighing 150mg of sodium borohydride solid, adding 5ml 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 18 hours, stirring magnetons and aqueous solution in the reaction system are removed, and 5ml of methanol solution dissolved with 100mg of sodium hexafluoroantimonate is added; and then, removing the organic solvent through a rotary evaporator, washing the organic solvent with methanol and toluene for several times respectively to remove redundant ligand and byproducts, finally dissolving the product in dichloromethane, diffusing n-hexane into dichloromethane solution by using a gas phase diffusion method, and obtaining red crystals after one week, namely the target product.
Example 2: characterization of the Crystal Structure
AuCu obtained in example 1 was used14The nanoclusters are further characterized by the following process:
under an optical microscope, red crystals are selected, and one crystal with better quality is selected to be tested under the protection of nitrogen atmosphere (170K). In the presence of Ga-K alpha
The 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 solved and refined in Olex2 software using ShelXT and ShelXL programs. All Au, Cu, N and S atoms are directly found, the remaining non-hydrogenAtoms 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 produced by the residual solvent molecules was removed from the data using the SQUEEZE method in PLATON, and the resulting data was again further refined. Detailed crystal data are shown in table 1 below.
TABLE 1 AuCu14Nanocluster primary crystallographic data
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 (3)
1. AuCu with high phosphorescence quantum yield in air atmosphere14Nanoclusters characterized by:
the AuCu14The nanocluster is an AuCu alloy nanocluster protected by mixed ligands, and comprises 1 Au atom, 14 Cu atoms, 12 4-tert-butyl thiophenol ligands and 6 bis (2-cyanoethyl) phenylphosphine ligands, and the periphery of the nanocluster is provided with an SbF6 -A counterion; the AuCu14The precise structure of the nanocluster contains an Au atomic core and a metal cage consisting of 14 cu (i) atoms.
2. AuCu according to claim 114Nanoclusters characterized by:
the AuCu14The molecular formula of the nanocluster is [ AuCu ]14(C10H13S)12(C12H13N2P)6](SbF6) Abbreviated as AuCu14Belongs to the triclinic system, the space group is P-1,
α＝83.358(7)°，β＝62.415(6)°，γ＝65.215(6)°，
3. a method for preparing an AuCu nanocluster according to claim 1 or 2, comprising the steps of:
firstly, adding a tetrabromo-gold sodium aqueous solution, tetraoctyl ammonium bromide and dichloromethane into a flask, and adding 4-tert-butyl thiophenol into a reaction system after 30 minutes; after 60 minutes of reaction, Cu (NO) was added3)2Dissolving in methanol and adding into a reaction system; after reacting for 30 minutes, adding bis (2-cyanoethyl) phenylphosphine; after 60 minutes, weighing sodium borohydride solid, adding deionized water to prepare a solution, directly and quickly adding the solution into the pear-shaped flask, and then immediately turning black the solution; after the reaction is continuously stirred for 18 hours, stirring magnetons and aqueous solution in the reaction system are removed, and methanol solution dissolved with sodium hexafluoroantimonate is added; and then removing the organic solvent by a rotary evaporator, washing by using methanol and toluene respectively to remove redundant ligand and byproducts, finally dissolving the product in dichloromethane, diffusing n-hexane into dichloromethane solution by using a gas phase diffusion method, and obtaining red crystals after one week, namely the target product.
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| CN115582552A (en) * | 2022-10-10 | 2023-01-10 | 武汉理工大学 | Preparation method for improving gold clusters based on solvent-assisted two-phase synthesis strategy |
| CN117102493A (en) * | 2023-07-18 | 2023-11-24 | 深圳大学 | Dissimilar metal gold copper cluster compound and preparation method and application thereof |
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| CN115537932A (en) * | 2022-09-28 | 2022-12-30 | 西北工业大学宁波研究院 | High-cadmium-doped core-shell Au 16 Cd 16 (SR) 20 Cluster and preparation method thereof |
| CN115537932B (en) * | 2022-09-28 | 2024-04-19 | 西北工业大学宁波研究院 | High-cadmium-doped core-shell Au16Cd16(SR)20Cluster and preparation method thereof |
| CN115582552A (en) * | 2022-10-10 | 2023-01-10 | 武汉理工大学 | Preparation method for improving gold clusters based on solvent-assisted two-phase synthesis strategy |
| CN115582552B (en) * | 2022-10-10 | 2023-10-27 | 武汉理工大学 | Preparation method for improving gold cluster based on solvent-assisted two-phase synthesis strategy |
| CN117102493A (en) * | 2023-07-18 | 2023-11-24 | 深圳大学 | Dissimilar metal gold copper cluster compound and preparation method and application thereof |
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