CN111606931B - Perfluoro glutaric acid protected octanuclear silver nanocluster with precise atomic structure and preparation method and application thereof - Google Patents
Perfluoro glutaric acid protected octanuclear silver nanocluster with precise atomic structure and preparation method and application thereof Download PDFInfo
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 66
- 239000004332 silver Substances 0.000 title claims abstract description 66
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 65
- CCUWGJDGLACFQT-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoropentanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(O)=O CCUWGJDGLACFQT-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 150000001450 anions Chemical group 0.000 claims description 4
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical class OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 210000002858 crystal cell Anatomy 0.000 claims 1
- 239000002356 single layer Substances 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 4
- 238000000799 fluorescence microscopy Methods 0.000 abstract description 4
- 101710134784 Agnoprotein Proteins 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000003993 interaction Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- -1 dimethylamine cations Chemical class 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000000547 structure data Methods 0.000 description 2
- LWAVGNJLLQSNNN-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-azidobenzoate Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C(=O)ON1C(=O)CCC1=O LWAVGNJLLQSNNN-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 101000878457 Macrocallista nimbosa FMRFamide Proteins 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 150000003958 selenols Chemical class 0.000 description 1
- OGFYIDCVDSATDC-UHFFFAOYSA-N silver silver Chemical compound [Ag].[Ag] OGFYIDCVDSATDC-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
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- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention provides an octanuclear silver nanocluster with a precise atomic structure and protected by perfluoroglutaric acid, which contains perfluoroglutaric acid and AgNO by heating under an alkaline condition3And (3) preparing a solution of N, N' -dimethylformamide. The core structure of the silver nanocluster is Ag with a rhombohedral structure8 6+It fluoresces yellow-green in THF solution at room temperature and orange-yellow in the solid state, which is unique in the structure of the monolayer of ligand-protected silver nanoclusters. The octanuclear silver nanocluster protected by perfluoroglutaric acid and having an accurate atomic structure has inherent biocompatibility and excellent fluorescence performance, and is favorable for being used as a luminescent molecule to be applied to the aspects of biological detection, cell marking, fluorescence imaging and the like.
Description
Technical Field
The invention belongs to the technical field of preparation and application of fluorescent functional nano materials, and particularly relates to an octanuclear silver nanocluster with an accurate atomic structure and protected by perfluoroglutaric acid, and a preparation method and application thereof.
Background
Monolayer ligand-protected atomic structure-accurate coin metal (Cu/Ag/Au) nanoclusters (CMNCs) are of interest due to their structural diversity and attractive special properties. Their formation and stabilization often rely on the protection of monolayer (organic or inorganic) ligands. These protective monolayer ligands play a key role in coin metal nanocluster structure formation and intrinsic properties. The monolayer protecting ligands are selected to construct novel monolayer protected metal nanocluster molecules, and the classical soft and hard acid-base theory (HSAB theory) should be followed. Numerous research results indicate that coinage metal atoms of the soft acid type tend to undergo strong coordination interactions with ligands of the soft base type to form stable coinage metal nanoclusters. Soft base ligands such as phosphines, thiols, selenols, alkynes, etc. are widely used to prepare CMNCs, where a large number of coin metal nanoclusters are constructed and isolated in the literature, and the molecular structures with precise atomic structures are characterized with a large number of precisions. However, attempts to construct coin metal nanoclusters using hard base ligands have often failed, and few examples of hard base ligand-protected CMNCs are reported in the literature, which are characterized by a single crystal structure and have precise atomic structures. The group q. -m.wang first characterized the all-nitrogen ligand (bipyramid anion, dpa) protected silver nanoclusters by a single crystal structure: [ Ag ]21(dpa)12]SbF6And [ Ag22(dpa)12](SbF6)2And elucidating their structure and light-responsive properties. Two examples of Ag with precise atomic structure protected by nitrogen/oxygen mixed ligand16And Ag8Nanoclusters have also been reported in the last year, such clusters exhibiting near infrared luminescent properties. In recent years, there has been only a sporadic trend for some inorganic total oxygen type ligand-protected silver nanoclusters. For example, yamaguchi et al, by deficiency of the polyacid [ SiW ]10O36]8-Successively build Ag6And Ag27Silver nanoclusters. Zhang Jian team reported a rare instance of Ag stabilized by titanyl clusters6Silver nanoclusters. It is apparent that the above examples are all silver nanoclusters protected with inorganic perhydroxy ligands, protected with organic perhydroxy ligands (e.g., organic carboxylic acids, etc.)The silver nanoclusters with precise atomic structures have not been reported in the literature.
Although organic carboxylic acids with low price and abundant varieties are used for constructing coin metal nanoparticles in large quantity, silver nanoclusters protected by carboxylic acids and having precise atomic structures are not reported in documents, and related researches can reveal carboxylic acid-protected face yarns with CMNCs structures and further enrich the varieties of the silver nanoclusters. Meanwhile, the inorganic total oxygen type ligand-protected silver nanoclusters do not have normal-temperature fluorescence performance, and discovery and related application of the fluorescence performance of the carboxylic acid-protected CMNCs are pioneered.
Disclosure of Invention
In view of this, the invention provides an octanuclear silver nanocluster with a perfluoroglutaric acid-protected atomic structure, so as to fill up the research blank of organic carboxylic acid protection CMNCs.
The invention also provides a preparation method of the octanuclear silver nanocluster with the perfluoroglutaric acid-protected atomic structure and the accurate atomic structure, and the preparation method is simple in preparation process, low in cost and mild in reaction conditions.
The invention also provides application of the perfluoroglutaric acid-protected eight-core silver nanocluster with an accurate atomic structure, and the octa-core silver nanocluster is used as a luminescent molecule and applied to the technical fields of biological detection, cell marking, fluorescence imaging and the like.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a perfluoroglutaric acid protected octanuclear silver nanocluster with an accurate atomic structure has a chemical formula: { [ (CH)3)2NH2]6[Ag8(pfga)6]}·H2O.6DMF, the perfluoroglutaric acid protected octanuclear silver nanocluster with an accurate atomic structure belongs to a trigonal system, a space group is R-3c, and unit cell parameters are as follows:
α＝90°，β＝90°，γ＝120°；
the perfluoroglutaric acid protectionThe octanuclear silver nanocluster with precise atomic structure is a silver nanocluster protected by a full carboxylic acid ligand, and the anion part of the cluster is [ Ag8(pfga)6]6-Unit, cluster core is Ag with rhombohedral structure8 6+(ii) a At room temperature, strong yellow-green fluorescence was emitted in THF solution, and orange-yellow fluorescence was emitted in the solid state.
The preparation method of the perfluoroglutaric acid-protected eight-core silver nanocluster with the precise atomic structure comprises the steps of heating perfluoroglutaric acid and AgNO under alkaline conditions3Was prepared from a solution of N, N' -dimethylformamide.
Preferably, perfluoroglutaric acid is added to AgNO3The N, N' -dimethylformamide solution is fully stirred, then the methanol solution of tetramethyl ammonium hydroxide is added, after heating and sealed storage for a plurality of hours, the solution is filtered and slowly evaporated to obtain yellow rhombic crystals, namely the octanuclear silver nanoclusters with precise atomic structures protected by the perfluoro glutaric acid.
Preferably, perfluoroglutaric acid is reacted with AgNO31 is 1.
Preferably, tetramethylammonium hydroxide is reacted with AgNO3Is 1.
Preferably, the heating and sealing storage is carried out for several hours, wherein the heating temperature is 50-80 ℃.
Preferably, the heating temperature is 70 ℃.
Preferably, the storage time is 12-36 h after being heated and sealed for storage for several hours.
Preferably, the storage time is 20h.
The application of the octanuclear silver nanocluster with the perfluoroglutaric acid-protected atomic structure precision is applied to biological detection, cell marking and fluorescence imaging.
By adopting the technical scheme, the invention has the beneficial effects that: the invention provides an octanuclear silver nanocluster with a precise atomic structure and protected by perfluoroglutaric acid, which contains perfluoroglutaric acid and AgNO by heating under an alkaline condition3N, N' -diAnd preparing a methyl formamide solution. The silver nanoclusters have rhombohedral Ag8 6+The core, which emits strong yellow-green fluorescence in THF solution and strong orange-yellow fluorescence in solid state, is unique in the monolayer protected silver cluster structure. The intrinsic biocompatibility and excellent fluorescence property of the octa-silver nanocluster protected by the perfluoroglutaric acid are beneficial to being applied to aspects such as biological detection, cell marking and fluorescence imaging as luminescent molecules.
Drawings
Fig. 1 is a schematic structural view of perfluoroglutaric acid-protected atomic structure-accurate eight-core silver nanoclusters.
FIG. 2 is a rhombohedral core Ag of perfluoroglutaric acid protected octanuclear silver nanoclusters with precise atomic structures8 6+The structure is schematic. The numbers in the figure indicate the bond length of silver-silver interaction.
FIG. 3 shows perfluoroglutaric acid and rhombohedral core Ag8 6+Schematic representation of coordination mode.
FIG. 4 shows a structure surrounding a cluster structure [ Ag ]8(pfga)6]6-Schematic of strong hydrogen bonding interactions with DMA counter ions and DMF solvent molecules. Wherein the dotted line represents a hydrogen bond.
Fig. 5 is an X-ray powder diffraction pattern of perfluoroglutaric acid protected atomic structure accurate octanuclear silver nanoclusters.
Fig. 6 is a solid uv diffuse reflectance spectrum of perfluoroglutaric acid protected atomic structure accurate octanuclear silver nanoclusters.
Fig. 7 is a solid bandgap diagram (2.54 eV) of perfluoroglutaric acid protected atomic structure-accurate eight-core silver nanoclusters.
Fig. 8 is a solid state fluorescence spectrum of perfluoroglutaric acid protected atomic structure accurate octanuclear silver nanoclusters.
Fig. 9 is a THF solution uv spectrum of perfluoroglutaric acid protected atomic structure accurate octanuclear silver nanoclusters.
Fig. 10 is a THF solution fluorescence spectrum of perfluoroglutaric acid protected atomic structure accurate octanuclear silver nanoclusters.
Fig. 11 is a full X-ray photoelectron spectrum of perfluoroglutaric acid protected atomic structure-accurate octanuclear silver nanoclusters.
FIG. 12 is an X-ray photoelectron spectroscopy Ag 3d of perfluoroglutaric acid protected octanuclear silver nanoclusters with precise atomic structure5/2Narrow scan.
FIG. 13 shows that perfluoroglutaric acid protected octanuclear silver nanoclusters with precise atomic structures are dissolved in acetone/CH2Cl2Positive ion mode ESI-MS Mass Spectroscopy in mixed solvent.
FIG. 14 is a graph comparing the isotope simulation and the observed value of species A, in which the molecular ion peak A =2568.46: [ M + H ]+]+.M＝{[(CH3)2NH2]6[Ag8(pfga)6]}。
FIG. 15 is a graph comparing the isotope simulation and the observed value of species B, wherein peak B =2608.48: [ M + H ]++2HF]+And 2613.52[ m + (CH ]3)2NH2]+。
FIG. 16 is a graph comparing the isotope simulation and the observed value of species C, wherein peak C =2648.49: [ M + H ]++4HF]-And 2653.60[ m ] +H++5NH3]-。
Detailed Description
The technical scheme and the technical effect of the invention are further elaborated in the following by combining the drawings of the invention.
In one embodiment, an Ag alloy with rhombohedral valences8 6+Core perfluoroglutaric acid (pfga) protected silver nanoclusters by heating under alkaline conditions containing perfluoroglutaric acid and AgNO3Is prepared from a solution of N, N' -Dimethylformamide (DMF). Specifically, perfluoroglutaric acid is added to AgNO3To the DMF solution of (1), stirring well, then adding tetramethylammonium hydroxide (Me)4NOH), heating, sealing and storing for a plurality of hours, filtering the solution, and slowly evaporating to obtain a yellow rhombic crystal, namely the octanuclear silver nanocluster with the accurate atomic structure and protected by the perfluorinated glutaric acid. Preferably, perfluoroglutaric acid is reacted with AgNO31, tetramethylammonium hydroxide to AgNO3The molar ratio of (1) to (6), the heating temperature is 50-80 ℃, and the preservation time is 12-36 h.
In a preferred embodiment, the synthesis process of the perfluoroglutaric acid-protected octanuclear silver nanocluster with precise atomic structure is shown as formula I, wherein Cluster 1 represents the perfluoroglutaric acid-protected octanuclear silver nanocluster with precise atomic structure, and the chemical formula is as follows: { [ (CH)3)2NH2]6[Ag8(pfga)6]}·H2O·6DMF。
The octanuclear silver nanocluster protected by perfluoroglutaric acid and having an accurate atomic structure belongs to a trigonal system, a space group is R-3c, and unit cell parameters are as follows:
α =90 °, β =90 °, γ =120 °. The detailed unit cell structure data are shown in table 1.
Table 1 unit cell structure data of the cluster compounds
aR1＝[Σabs(abs(Fo)-abs(Fc))]/[Σabs(Fo)].bwR2＝[Σ(w(Fo2-Fc2)2)/Σ[w(Fo2)2]0.5.
Referring to fig. 1 to 4, the perfluoroglutaric acid-protected, atomically precise octanuclear silver nanoclusters are all-carboxylic acid-protected silver nanoclusters having a cluster anion structural unit of [ Ag ]8(pfga)6]6-Core of its clusterIs Ag8 6+Rhombohedral, peripherally surrounded by six perfluoroglutaric acid ligands through cis μ4-η1,η1,η1,η1In which the length of the Ag-O bond is in
Within the range. In anionic nanoclusters [ Ag8(pfga)6]6-Six dimethylamine cations were observed as counter ions around, and were located at the six corners of the rhombohedra. In addition to electrostatic interactions, dimethylamine cations were also observed to form strong N-H.O hydrogen bond interactions with oxygen on pfga/DMF, which provide additional stability to nanoclusters. Referring to fig. 5, we measured the mass of crystalline powder produced by X-ray powder diffraction and demonstrated that the cluster was of high purity and could be produced in bulk in the same batch by simulated comparison with single crystal data.
Referring to fig. 6 to 7, the perfluoroglutaric acid-protected, atomically precise octanuclear silver nanocluster has a strong spectral absorption in the solid state with an energy band of 2.54eV, which is consistent with the crystal color (yellow) of the cluster. Referring to fig. 8, the perfluoroglutaric acid-protected octanuclear silver nanocluster with precise atomic structure emits orange fluorescence in solid state at normal temperature, with the maximum emission peak at 612nm and a small emission peak at 471nm.
At room temperature, the octanuclear silver nanocluster with the perfluoroglutaric acid protected atomic structure being accurate can be dissolved in a THF solution and shows good solution stability. Please refer to fig. 9, the ultraviolet absorption peaks are respectively λmax=263 and 378nm, molar absorbances 92236.74 and 55495.77L · mol, respectively-1·cm-1. Referring to FIG. 10, the cluster compound emits strong yellow-green fluorescence in THF solution at room temperature, and the maximum emission peak is located
A shoulder appeared at 608 nm.
Referring to FIGS. 11 and 12, the presence of each element in the molecular formula of the cluster was confirmed by measuring the X-ray photoelectron spectroscopy of the cluster by the corresponding element Ag 3d5/2The narrow sweep of the orbitals indicates that the cluster is AgI/Ag0Mixed valence compounds, in which the ratio of monovalent silver to zero valence silver is 38 6+The existence of a core. Referring to FIGS. 13-16, it was further confirmed by mass spectrometry that the cluster molecule is { [ (CH)3)2NH2]6[Ag8(pfga)6]The cluster compound exists stably in the solution, and the cluster compound molecule is further proved to contain two zero-valent silver.
At room temperature, the cluster compound is a strong luminophor no matter in a solution or a solid state, and the inherent biocompatibility and excellent luminescence property of the cluster compound are favorable for the application of the cluster compound as a molecular fluorescent probe in the research and practice of the biological field.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (6)
1. An octanuclear silver nanocluster protected by perfluoroglutaric acid and having an accurate atomic structure is characterized in that the octanuclear silver nanocluster has the chemical formula: { [ (CH)3)2NH2]6[Ag8(pfga)6]}•H2O.6DMF, wherein pfga is perfluoroglutaric acid, the octanuclear silver nanocluster with precise atomic structure protected by perfluoroglutaric acid belongs to a trigonal system, the space group is R-3c, and the parameters of a crystal cell are as follows:
a =14.3160(5) Å，b =14.3160(5) Å，c =86.613(5)Å，α=90°，β=90°，γ =120°；
the perfluoroglutaric acid-protected octanuclear silver nanocluster with an accurate atomic structure is a full carboxylate-protected silver nanocluster, and the anion part of the nanocluster is [ Ag ]8(pfga)6]6-The unit and the cluster core are provided with rhombus bodiesAg of structure8 6+(ii) a At room temperature, strong yellow-green fluorescence was emitted in THF solution, and orange-yellow fluorescence was emitted in the solid state.
2. A method of preparing perfluoroglutaric acid-protected, atomically accurate, octanuclear silver nanoclusters according to claim 1, wherein: perfluoroglutaric acid to AgNO3The N, N' -dimethylformamide solution is fully stirred, then the methanol solution of tetramethyl ammonium hydroxide is added, after heating and sealed storage for a plurality of hours, the solution is filtered and slowly evaporated to obtain yellow rhombic crystals, namely the octanuclear silver nanoclusters protected by the perfluoro glutaric acid and having accurate atomic structures; wherein, the perfluorinated glutaric acid and AgNO31, tetramethylammonium hydroxide to AgNO31.
3. The method of preparing perfluoroglutaric acid protected octanuclear silver nanoclusters with precise atomic structure according to claim 2, wherein said heating temperature is 50 ℃ to 80 ℃ after heating and storing in a sealed environment for several hours.
4. The method of preparing perfluoroglutaric acid-protected, atomically accurate, octanuclear silver nanoclusters according to claim 3, wherein the heating temperature is 70 ℃.
5. The method for preparing the perfluoroglutaric acid-protected octanuclear silver nanoclusters having an accurate atomic structure according to claim 2, wherein the storage time is 12 to 36 hours, after the storage under heat and sealing for several hours.
6. The method of preparing perfluoroglutaric acid-protected, atomically accurate, octanuclear silver nanoclusters according to claim 5, wherein the storage time is 20 hours.
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