CN116284836A - Metal gel and preparation method thereof - Google Patents
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000001879 gelation Methods 0.000 title description 3
- 239000010931 gold Substances 0.000 claims abstract description 75
- 239000002243 precursor Substances 0.000 claims abstract description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- -1 silver hexafluorophosphate Chemical compound 0.000 claims abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- HPHZVOOLJMXCIA-UHFFFAOYSA-K thiolane;trichlorogold Chemical compound [Cl-].[Cl-].[Cl-].[Au+3].C1CCSC1 HPHZVOOLJMXCIA-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000012769 display material Substances 0.000 claims description 3
- NRCLMYRLGIMSIX-UHFFFAOYSA-N ethyl 5-(hydroxymethyl)-1h-pyrazole-3-carboxylate Chemical compound CCOC(=O)C1=CC(CO)=NN1 NRCLMYRLGIMSIX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
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- 239000003292 glue Substances 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 72
- 239000013078 crystal Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 238000006862 quantum yield reaction Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- KJTRXVXWSSPHRV-UHFFFAOYSA-N 4-benzoyl-5-methyl-2-phenyl-1h-pyrazol-3-one Chemical compound O=C1C(C(=O)C=2C=CC=CC=2)=C(C)NN1C1=CC=CC=C1 KJTRXVXWSSPHRV-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 4
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 230000005291 magnetic effect Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910002696 Ag-Au Inorganic materials 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
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- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
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- AFVLVVWMAFSXCK-UHFFFAOYSA-N α-cyano-4-hydroxycinnamic acid Chemical compound OC(=O)C(C#N)=CC1=CC=C(O)C=C1 AFVLVVWMAFSXCK-UHFFFAOYSA-N 0.000 description 2
- 229910002695 AgAu Inorganic materials 0.000 description 1
- 229910002703 Al K Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
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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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
Abstract
The invention discloses a metal gel and a preparation method thereof, and belongs to the technical field of functional composite materials. The preparation method of the metal gel comprises the following steps: (1) Dissolving an organic ligand and tetrahydrothiophene gold chloride in an organic solvent, then adding triethylamine, uniformly stirring, adding n-hexane for precipitation, and obtaining a precipitation product, namely a precursor Au 3 The method comprises the steps of carrying out a first treatment on the surface of the (2) Precursor Au 3 And silver hexafluorophosphate are respectively dissolved in an organic solvent to obtain a precursor Au 3 Solution and silver hexafluorophosphate solution, and then the silver hexafluorophosphate solution is added dropwise to the precursor Au 3 And in the solution, the obtained precipitate is the metal gel. The metal gel has the characteristics of simple preparation, low molecular weight, no long-chain structure, accurate molecular structure and the like, and is a metal gel constructed by only relying on metal-metal bond action and hydrogen bondAnd (5) glue.
Description
Technical Field
The invention relates to the technical field of functional composite materials, in particular to a metal gel and a preparation method thereof.
Background
The metal gel is one of supermolecular gel materials, and has special optical, magnetic, catalytic and other characteristics compared with gel formed by organic matters and polymers, so that the metal gel has great application potential. Metal gels are generally composed of metal complexes together through metal-metal bonds and various supermolecular interactions, so in order to obtain a shape stable metal gel, long chain hydrophilic or hydrophobic groups are typically introduced into the ligand to form a network structure (nat. Chem., 2009, 1, 437-442) and encapsulate more solvent molecules. However, the molecular weight of the gel is often too large as a result of the above, the exertion of the characteristics of the metal gel is limited, and the synthetic modification and flexible regulation of the material are greatly reduced.
Disclosure of Invention
The invention aims to provide a metal gel and a preparation method thereof, which are used for solving the problems in the prior art. The metal gel has the characteristics of low molecular weight, no long-chain structure and the like, and is constructed by only relying on metal-metal bond action and hydrogen bond.
The metal gel is prepared from low molecular weight gel (low molecular weight gelators, LMWG) and Au 6 Ag is prepared by self-assembling to generate a one-dimensional supermolecular chain structure, so as to form a gel network. The gel has the characteristics of low molecular weight, simple structure, easy preparation, reversible and adjustable property and good biocompatibility. The use of metal complexes as low molecular weight gels also has the significant specific advantage of having both the photo, electro, stimulus response characteristics characteristic of the coordinating supramolecular polymer, and the morphology of the supramolecular gel "soft material". In addition, the soft substances assembled by virtue of supermolecule action can realize conversion of different structures and functions by regulating the triggering condition of gelation by various physical and chemical means. Furthermore, metal complex gels generally also have good crystallinity, which is very advantageous for the characterization of their microstructure and for the construction of structure-property relationships. However, most inorganic or metallic gels today rely solely on intermolecular interactions to achieve assembly, resulting in gel materials with poor stability and easy crystallization, so that long chain groups with hydrophilic/hydrophobic character are typically introduced to enhance crosslinking, stabilizing the gel. However, the disadvantage of this is that the molecular weight of the small molecular gel is increased, and the characteristic of flexible regulation and control properties is sacrificed. The invention relies on metal-metal actionMultiple hydrogen bonds, formed metal gels, clear structure and chemical composition, exist in both solution and solid state and can be characterized.
In order to achieve the above object, the present invention provides the following solutions:
one of the technical schemes of the invention is as follows: a metal gel, the structural formula of which is shown as formula (1):
formula (1).
The second technical scheme of the invention is as follows: the preparation method of the metal gel with the structure of the formula (1) comprises the following steps:
(1) Dissolving an organic ligand and tetrahydrothiophene gold chloride in an organic solvent, then adding triethylamine, uniformly stirring, adding n-hexane for precipitation, and obtaining a precipitation product, namely a precursor Au 3 （（AuL 2 ） 3 ）；
Precursor Au 3 Is 5- (hydroxymethyl) pyrazole-3 ethyl formate trinuclear gold complex;
triethylamine is a weak base, which can remove protons connected by N on pyrazole ligand to form a structure of coordination of pyrazole and two metals.
Precursor Au 3 The structural formula of (2) is shown as the formula:
formula (2);
(2) Precursor Au 3 And silver salt are respectively dissolved in an organic solvent to obtain a precursor Au 3 Solution and silver salt solution, then the silver salt solution is dripped into the precursor Au 3 In the solution, the obtained precipitate is the metal gel (Au 6 Ag, green gel solid, green light emitted by ultraviolet lamp);
the precursor Au 3 And silver salt is more than or equal to 2:1.
Au 6 Ag is Au 3 Au formed with Ag ions 3 -Ag-Au 3 Sandwich type supermolecule complexes.
Further, in step (1), the organic ligand is ethyl 5- (hydroxymethyl) pyrazole-3 carboxylate.
Further, in the step (1), the molar ratio of the organic ligand to the tetrahydrothiophene gold chloride is 1:1.
Further, in the step (1), the organic solvent is ethanol and acetone with a volume ratio of 1:1.
Further, in the step (1), the stirring time is 30min.
Further, in the step (2), the organic solvent is dichloromethane; the silver salt is silver hexafluorophosphate.
The third technical scheme of the invention: the application of the metal gel in the optical functional material or the display material.
The invention discloses the following technical effects:
(1) The metal gel has the characteristics of low molecular weight, no long-chain structure and the like, and is constructed by only relying on metal-metal bond action and hydrogen bond.
(2) The metal gel in the invention can be converted in solid state (gel state solvent volatilized), gel state and solution state (gel state is dissolved in a large amount of organic solvents), has excellent luminescence performance, simple synthesis process flow and strong operability, and has wide application prospect as a light functional material.
(3) The preparation method of the metal gel is extremely simple, and is different from the long-time aging process required for preparing the gel by a solution-gel method. Precursor Au prepared by the invention 3 Has definite molecular structure and molecular weight, can be characterized by adopting the conventional characterization method of organic matters and complexes, and is a precursor Au 3 In the preparation process, the solvent can be used for preparing crystals, so that the purification time and cost of the precursor prepared by synthesis are greatly reduced.
(4) The present invention provides a method for preparing a low molecular weight metal gel, but the raw materials used are not limited to the metals and organic ligands mentioned in the present invention. The organic ligand is replaced, and the preparation of the metal gel with the sandwich structure can be realized by modification.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a metal gel Au prepared in example 1 of the present invention 6 Schematic space structure of Ag;
FIG. 2 shows a metal gel Au prepared in example 1 of the present invention 6 Scanning electron microscope images of Ag;
FIG. 3 shows a metal gel Au prepared in example 1 of the present invention 6 A transmission electron microscope image of Ag;
FIG. 4 shows a metal gel Au prepared in example 1 of the present invention 6 A physical diagram of Ag;
FIG. 5 shows the precursor Au prepared in example 1 of the present invention 3 And metal gel Au 6 Powder X-ray diffraction pattern of Ag;
FIG. 6 shows a metal gel Au prepared in example 1 of the present invention 6 Infrared spectrogram of Ag;
FIG. 7 shows a metal gel Au prepared in example 1 of the present invention 6 Mass spectrum of Ag;
FIG. 8 shows a metal gel Au prepared in example 1 of the present invention 6 A two-dimensional nuclear magnetic spectrogram of Ag;
FIG. 9 shows a metal gel Au prepared in example 1 of the present invention 6 An X-ray photoelectron spectrum of Ag, wherein A is a 3d orbit of Ag and B is a 4f orbit of Au;
FIG. 10A metal gel Au prepared in example 1 of the present invention 6 Excitation spectrum, photoluminescence spectrum, luminescence color and quantum yield of Ag;
FIG. 11 shows a metal gel Au prepared in example 1 of the present invention 6 Ag is in sunlight, white light of LED flashlightAnd a luminescent photo under 365nm ultraviolet light irradiation;
FIG. 12 shows a metal gel Au prepared in example 1 of the present invention 6 A CIE color graph of Ag;
FIG. 13 shows the precursor Au prepared in comparative example 1 of the present invention 3 -2, wherein the left diagram is the molecular structure and the right diagram is the crystal structure;
FIG. 14 shows Au prepared in comparative example 1 of the present invention 6 Schematic diagrams of molecular structure and crystal structure of Ag-2, wherein the left diagram is the molecular structure, and the right diagram is the crystal structure;
FIG. 15 shows Au prepared in comparative example 1 of the present invention 6 Crystal morphology of Ag-2 under different light.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
A metal gel (Au) 6 Ag), the preparation method:
(1) Dissolving ligand 5- (hydroxymethyl) pyrazole-3 ethyl formate (9 mg,0.05 mmol) and tetrahydrothiophene gold chloride (16 mg,0.05 mmol) in a mixed solution of 15mL ethanol and 15mL acetone, carrying out ultrasonic treatment until the ligand 5- (hydroxymethyl) pyrazole-3 ethyl formate is completely dissolved to obtain a mixed solution, adding 1mL triethylamine into the mixed solution, and stirring at room temperature for 30min to obtain a clear and transparent solution; adding enough n-hexane into the clear and transparent solution until the white precipitate is completely separated out, filtering the white precipitate, washing with ethanol, and drying to obtain a precursor Au 3 (trinuclear gold 5- (hydroxymethyl) pyrazole-3 ethyl formate complex, (AuL) 2 ） 3 ) Molecular weight: 1098.08.
precursor Au 3 The structural formula is as follows:
(2) Precursor Au 3 (66 mg,0.06 mmol) was added to 3mL of methylene chloride and the mixture was sonicated until complete dissolution to give Au precursor 3 A solution; silver hexafluorophosphate (8 mg,0.03 mmol) was added to 3mL of dichloromethane and sonicated until complete dissolution, yielding a silver hexafluorophosphate solution; then slowly injecting the hexafluorophosphate silver solution into the precursor Au by using a dropper 3 In the solution, a green gel-like solid immediately appeared, namely a metal gel (Au 6 Ag，Au 3 Au formed with Ag ions 3 -Ag-Au 3 Sandwich type superdivisionSub-complex), repeating unit molecular weight: 2303.07, the structural formula is as follows:
the metal gel Au prepared in this example 6 The space structure of Ag is schematically shown in FIG. 1, the Scanning Electron Microscope (SEM) is shown in FIG. 2, and the Transmission Electron Microscope (TEM) is shown in FIG. 3.
As can be seen from FIGS. 2 and 3, the metal gel Au prepared in this example 6 Ag has a network structure and a gel state.
The metal gel Au prepared in this example 6 The physical diagram of Ag is shown in FIG. 4.
Precursor Au prepared in this example 3 （（AuL 2 ） 3 ) And metal gel Au 6 The powder X-ray diffraction pattern of Ag is shown in fig. 5.
The X-ray diffraction characterization method comprises the following steps: powder diffraction data collection was performed on a bruker D8 advance diffractometer operating at 40KV and 40mA current using graphite-monochromatized copper target X-ray (Cu K)a，λ=1.5418 a), the continuous scanning is completed in the range of 3 ° to 40 °. The single crystal structure powder diffraction spectrum simulated transformation uses Mercury software.
As can be seen from FIG. 5, au 6 Ag has good crystallinity.
The metal gel Au prepared in this example 6 The infrared spectrum of Ag is shown in FIG. 6.
Infrared spectrometry: KBr-based 400-4000 cm using a Nicolet image 410FTIR spectrometer −1 FT-IR (Potassium bromide tablet, cm −1 )：3140w, 2980m, 2934w, 1711s, 1524m, 1471m, 1437m, 1385m, 1247s, 1186s, 1079m, 1049m, 1030m, 845w, 818w, 767m。
The metal gel Au prepared in this example 6 The mass spectrum of Ag is shown in FIG. 7.
Mass spectrum measurement: measured using a Applied Biosystems 4800 Plus MALDI TOF Analyzer (ABI) spectrometer under an alpha-cyano-4-hydroxycinnamic acid matrix. MALDI-TOF-MS (alpha-cyano-4-hydroxycinnamic acid matrix).
From FIG. 7, a strong signal peak with a mass-to-core ratio of 2304.93 is observed, which is a component { Ag [ (AuL) 2 ) 3 ] 2 } + Molecular ion peaks of (2).
The metal gel Au prepared in this example 6 The two-dimensional nuclear magnetic spectrum of Ag is shown in FIG. 8.
Two-dimensional nuclear magnetic spectrometry: adopting Bruker Biospin Avance MHz and Au with the wavelength of 52400 MHz 6 Ag was dissolved in deuterated chloroform reagent for testing.
As can be seen from FIG. 8, au 6 Au on upper and lower bottom surfaces of Ag sandwich structure 3 The protons of the molecules are coupled to each other, indicating the formation of multiple hydrogen bonds between the molecules.
The metal gel Au prepared in this example 6 The X-ray photoelectron spectrum of Ag is shown in FIG. 9. In fig. 9, a is a 3d track of Ag and B is a 4f track of Au.
X-ray photoelectron spectroscopy (XPS) measurement: using the spectrum of the X-ray photoelectron of ESCALAB 250Xi of Sieimer technology company (Thermo Fisher Scientific) in the United states, single-color Al K alpha (hν= 1486.6 eV), 150W of power, 500 μm beam spot; binding energy was calibrated with C1s 284.8 eV.
The metal gel Au prepared in this example 6 The excitation spectrum, photoluminescence spectrum (solution/gel/solid), luminescence color and quantum yield of Ag are shown in fig. 10.
The metal gel Au prepared in this example 6 The luminescence photo of Ag under the irradiation of sunlight, white light of an LED flashlight and 365nm ultraviolet light is shown in FIG. 11.
The metal gel Au prepared in this example 6 The CIE color graph of Ag is shown in fig. 12.
The structure of the metal gel Au6Ag prepared by the embodiment can be characterized by mass spectrogram, two-dimensional nuclear magnetic resonance spectrogram and theoretical calculation, and the result shows that Au 6 Ag presents Au 3 AgAu 3 Is composed of sandwich structure composed of Au-Ag metal-metal bond interaction and intermolecular multiple hydrogen bonds. The polymer has a network structure under SEM and TEM, can form stable organic gel with solvents such as dichloromethane and the like, and further research shows that,the gel can emit green light under the irradiation of ultraviolet light, sunlight and incandescent lamp (see figure 11), and has extremely high luminous quantum yield (more than 96%) under the excitation of ultraviolet light.
Au prepared in this example 6 Ag has photoluminescent properties, and exhibits relatively pure green light at normal temperature (0.21,0.46) (excitation light wavelength 360 nm) (fig. 12), with a solid quantum yield of 57.1%, a quantum yield of gel and solution states as high as 95% (excitation light wavelength 360 nm), and particularly with a very low concentration (0.01 mmol/L) in methylene chloride solution, a quantum yield as high as 99.7% (excitation light wavelength 360 nm). Furthermore, they can maintain the same emission wavelength and high quantum yield in aprotic solvents such as acetone, tetrahydrofuran, n-hexane. These results all show Au 6 Ag has extremely strong application prospects of luminescent and display materials.
Comparative example 1
The ligand bis-3, 5- (ethoxycarbonyl) 2-1H-pyrazole (10.6 mg,0.05 mmol) and tetrahydrothiophene gold chloride (16 mg,0.05 mmol) were dissolved in 15mL of ethanol and 30mL of acetone, respectively, and an acetone solution of tetrahydrothiophene gold chloride was added to the ethanol solution of the ligand. After a few drops of anhydrous triethylamine were added to the mixed solution, a white precipitate was formed immediately, and the suspension was stirred for another 15 minutes to complete the reaction. The white precipitate was collected by filtration, washed with methanol, acetone and diethyl ether (3X 1mL each) to give the precursor Au 3 -2。
Precursor Au 3 2 (77 mg,0.06 mmol) and silver hexafluorophosphate (8 mg,0.03 mmol) were added to 10mL of dichloromethane and stirred at room temperature for 30min to give a green suspension which was filtered to give a green transparent solution. Diffusing n-hexane/diethyl ether (volume ratio of 3:2) into the green transparent solution by gas diffusion to obtain green needle-like crystal, au 6 Ag-2。
Precursor Au prepared in this comparative example 3 The molecular and crystal structure of-2 are schematically shown in FIG. 13.
Au prepared in this comparative example 6 The molecular structure and crystal structure of Ag-2 are schematically shown in FIG. 14.
Au prepared in this comparative example 6 The crystal morphology of Ag-2 under different light is shown in FIG. 15.
As can be seen from FIG. 15, au prepared in this comparative example 6 Ag-2 is a needle-like crystalline material and is not a metal gel material, and Au cannot be realized by adopting the method of the comparative example 6 And (3) preparing Ag metal gel.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (8)
1. The metal gel is characterized by having a structural formula shown in a formula (1):
2. A method of preparing a metal gel according to claim 1, comprising the steps of:
(1) Dissolving an organic ligand and tetrahydrothiophene gold chloride in an organic solvent, then adding triethylamine, uniformly stirring, adding n-hexane for precipitation, and obtaining a precipitation product, namely a precursor Au 3 ；
(2) Precursor Au 3 And silver salt are respectively dissolved in an organic solvent to obtain a precursor Au 3 Solution and silver salt solution, then the silver salt solution is dripped into the precursor Au 3 In the solution, the obtained precipitate is the metal gel;
the precursor Au 3 And silver salt is more than or equal to 2:1.
3. The method of preparing a metal gel according to claim 2, wherein in the step (1), the organic ligand is ethyl 5- (hydroxymethyl) pyrazole-3 carboxylate.
4. The method of claim 2, wherein in step (1), the molar ratio of the organic ligand to the tetrahydrothiophene gold chloride is 1:1.
5. The method of claim 2, wherein in step (1), the organic solvent is ethanol and acetone in a volume ratio of 1:1.
6. The method of preparing a metal gel according to claim 2, wherein in the step (1), the stirring time is 30min.
7. The method of preparing a metal gel according to claim 2, wherein in step (2), the organic solvent is methylene chloride; the silver salt is silver hexafluorophosphate.
8. Use of the metal gel of claim 1 in a photofunctional material or a display material.
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| CN105936636A (en) * | 2016-05-06 | 2016-09-14 | 西北师范大学 | Preparation methods and application of long chain-containing phenazine derivative gel factor and metal gel thereof |
| US20170333886A1 (en) * | 2016-05-05 | 2017-11-23 | University Of North Texas | Metal-inorganic frameworks |
| CN109320454A (en) * | 2018-11-29 | 2019-02-12 | 西北师范大学 | The preparation and application of a kind of bi-component supramolecular organogel and its metal gel |
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| US20170333886A1 (en) * | 2016-05-05 | 2017-11-23 | University Of North Texas | Metal-inorganic frameworks |
| CN105936636A (en) * | 2016-05-06 | 2016-09-14 | 西北师范大学 | Preparation methods and application of long chain-containing phenazine derivative gel factor and metal gel thereof |
| CN109320454A (en) * | 2018-11-29 | 2019-02-12 | 西北师范大学 | The preparation and application of a kind of bi-component supramolecular organogel and its metal gel |
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