Polydentate heterocyclic coordination gold-silver type II cluster as well as preparation method and application thereof

Abstract

The invention provides a polydentate heterocyclic coordination gold-silver type II cluster as well as a preparation method and application thereof, and belongs to the technical field of optical waveguide materials. According to the invention, sulfur and nitrogen heteroatoms in the polydentate heterocyclic ring ligand and gold and silver salt are subjected to a coordination reaction, and gold and silver alloying can adjust the chemical / physical properties of the homogeneous metal nanocluster and improve the luminous efficiency; the high crystallinity and high luminous efficiency of the multi-tooth heterocyclic ring coordinated gold-silver type II cluster crystal can effectively reduce optical loss, improve optical waveguide performance and broaden an optical waveguide material system.

Description

Technical Field

[0001] The present invention relates to the technical field of optical waveguide materials, and in particular to a multi-dentate heterocyclic coordinated gold-silver type II cluster, a preparation method thereof, and application in optical waveguide materials. Background Art

[0002] Optical waveguides are one of the important components of miniaturized integrated nanophotonic devices. They are physical structures used to guide light in a specific direction and act as a "light pipe" there. Commercial optical fibers are much thicker than a human hair (460 mm) and are made of silica or transparent polymers. All industrial optical waveguides are composed of silica or transparent polymers and have dimensions larger than the nano / submicro domain. In contrast, the goal of nanophotonics is to shrink existing photonic devices to the nano / micro scale, which is 100 times smaller than a human hair. Nano / microscale optical waveguides are one of the key components for guiding and manipulating light in miniaturized photonic devices. Based on their composition, optical waveguides are divided into four categories: (1) metal plasma waveguides; (2) inorganic semiconductor waveguides; (3) polymer dielectric waveguides; and (4) organic waveguides. Based on the properties of the light waves they propagate, organic waveguides are further divided into active or passive waveguides. In active organic waveguides, electronic excitations of π-conjugated organic solids lead to coupled exciton-polaritons (excitons: electron-hole pairs; polarons: coupling of electromagnetic radiation to exciton pairs) along a one-dimensional organic solid. Passive organic waveguides propagate light directly from the source input to the output. Recent recognition of the waveguide behavior of organic structures with dimensions approaching the wavelength of light has created a highly innovative and challenging research area, leading to the creation of a new research field at the interface between organic materials chemistry and optics, namely "organic photoconductors" or "organic optical waveguides." Compared to inorganic materials, the optical and optoelectronic properties of organic solid materials rely solely on weak intermolecular interactions such as hydrogen bonding, π-π stacking, van der Waals forces, and charge transfer interactions. Well-ordered solid organic molecules have been shown to exhibit very high charge carrier mobility. Compared to polymers, a wide variety of functional organic molecules with tailored properties, such as their physical state, molecular weight, solubility, flexibility, supramolecular groups, conjugation, symmetry, polarizability, refractive index, optical, optoelectronic, and magnetic properties, are readily accessible through laboratory organic synthesis. Organic optical waveguide materials have diverse structures and photophysical properties such as low optical loss, and have broad application potential in the field of optics. From the perspective of practical applications, the development of optical waveguide materials is of great significance to information transmission in modern society.

[0003] Metal nanoclusters, particularly ligand-stabilized noble metal nanoclusters, have rapidly developed over the past few years due to their atomically precise structures, quantum size effects, and discrete electronic energy levels. These features make these nanomaterials attractive for studying structure-property correlations. Due to their atomically precise structures and intriguing chemical / physical properties, metal nanoclusters are an emerging class of modular nanomaterials. Photoluminescence (PL) is one of their most fascinating properties, resulting in a plethora of promising PL-based applications, such as chemical sensing, bioimaging, cell labeling, phototherapy, and drug delivery. However, the luminescence efficiency of most current nanoclusters remains unsatisfactory, with relatively low luminescence quantum yields (PLQYs) (typically below 20%), emission lifetimes typically in the nanosecond range, and an invariably red emission color (emission wavelength above 630 nm). Therefore, alloying the metal core could be a promising approach to address these challenges. As a versatile strategy, alloying can significantly improve the physicochemical properties of these nanoclusters compared to their homogeneous counterparts, thus facilitating the application of these nanomaterials. Doping homo-gold and homo-silver nanoclusters with heteroatoms has been demonstrated to be a versatile approach to tune their physicochemical properties. Gold-silver alloying can also tune the chemical / physical properties of homogeneous metal nanoclusters, including optical, electrochemical, magnetic, and chirality, as well as stability and reactivity, which are indispensable for a wide range of applications in bioimaging, biosensing, chemical sensing, stimuli-responsive, and emissive coatings.

[0004] The various performances of gold-silver alloy clusters as optical waveguide materials still need to be improved. Therefore, further research is needed to synthesize gold-silver alloy clusters so that their various luminescence performances as optical waveguide materials can be optimized and improved. Summary of the Invention

[0005] In view of this, in order to solve the technical problem in the prior art that the various performances of gold-silver alloy clusters as optical waveguide materials still need to be improved, in the first aspect, the present invention provides a multi-tooth heterocyclic coordinated gold-silver type II cluster. The synergistic effect of the gold and silver atoms in the multi-tooth heterocyclic coordinated gold-silver type II cluster can enhance the luminescence performance, achieve high luminescence quantum efficiency, improve the optical waveguide performance and broaden the optical waveguide material system.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A polydentate heterocyclic coordinated gold-silver type II cluster having the following structure:

[0008]

[0009] Wherein, R is H, halogen or alkyl, the halogen is fluorine, chlorine, bromine or iodine, the alkyl is an alkyl containing C1-C6 carbon atoms, preferably an alkyl containing C1-C3 carbon atoms, and R is preferably hydrogen, fluorine or methyl, more preferably fluorine.

[0010] In a second aspect, the present invention also provides a method for preparing the above-mentioned multi-dentate heterocyclic coordinated gold-silver type II cluster, which is obtained by coordination reaction of sulfur and nitrogen heteroatoms in the multi-dentate heterocyclic ligand with gold and silver salts.

[0011] In a third aspect, the present invention also provides the use of the above-mentioned multi-dentate heterocyclic coordinated gold-silver type II cluster in optical waveguide materials.

[0012] The present invention provides a multi-tooth heterocyclic coordinated gold-silver type II cluster for use in optical waveguide materials. The multi-tooth heterocyclic ligand is synthesized through design, and the cluster is formed by a coordination reaction between the sulfur and nitrogen heteroatoms in the multi-tooth heterocyclic ligand and gold and silver salts. The synergistic effect of the gold and silver atoms in the multi-tooth heterocyclic coordinated gold-silver type II cluster can enhance luminescence performance, achieve high luminescence quantum efficiency, improve optical waveguide performance, and broaden the range of optical waveguide material systems. Compared with existing technologies, this invention has the following beneficial effects:

[0013] (1) The multi-toothed heterocyclic-coordinated gold-silver type II cluster optical waveguide material of the present invention has the unique ability to achieve high photoluminescence quantum yield (PLQY), effectively solving the luminescence efficiency issues commonly encountered by most current metal clusters. The development and application of this material significantly improves the performance of optical waveguide technology and brings new breakthroughs to the field of optoelectronics.

[0014] (2) In the present invention, a multidentate coordination strategy is adopted to enhance the spin-orbit coupling effect between the ligand and the metal. In this way, the S1 state and T1 state of the cluster are mainly dominated by the metal-to-ligand charge transfer (MLCT) process. In addition, among these clusters, the part with the non-radiative triplet cluster as the core has little effect on the overall luminescence performance and can be almost ignored. This discovery is of great significance for improving the emission efficiency of the cluster. At the same time, by modifying the donor and acceptor parts on the benzene ring, the luminescence color of the cluster is successfully adjusted to meet different application requirements.

[0015] (3) The multi-tooth heterocyclic coordinated gold-silver type II cluster optical waveguide material involved in the present invention has the significant advantage of achieving a low optical loss coefficient. This material has important application value in the field of optical waveguide technology and can effectively reduce energy loss during optical signal transmission, thereby improving the performance and efficiency of the entire optical communication system. The carefully designed and synthesized multi-tooth heterocyclic coordinated gold-silver type II cluster not only has unique structural stability, but also exhibits excellent optical properties in terms of function, making it a highly promising research direction in the field of optical waveguide materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The ultraviolet spectrum and fluorescence spectrum of the multi-dentate heterocyclic coordinated gold-silver type II cluster optical waveguide material I according to Example 1 of the present invention are shown;

[0017] Figure 2 The ultraviolet spectrum and fluorescence spectrum of the multi-dentate heterocyclic coordinated gold-silver type II cluster optical waveguide material II according to Example 2 of the present invention are shown;

[0018] Figure 3 The UV spectrum and fluorescence spectrum of the multi-dentate heterocyclic coordinated gold-silver type II cluster optical waveguide material III of Example 3 of the present invention are shown;

[0019] Figure 4 The ultraviolet spectrum and fluorescence spectrum of the multi-dentate heterocyclic coordinated gold-silver type II cluster optical waveguide material IV of Example 4 of the present invention are shown;

[0020] Figure 5 The optically resolved Hochsler spectra of the multi-dentate heterocyclic coordinated gold-silver type II cluster optical waveguide material I in Example 1 of the present invention at different excitation light points and edge spacings are shown;

[0021] Figure 6 A graph showing the ratio of the intensity of the crystal top and the main body to the distance between the top excitation point and the emission point of the multi-dentate heterocyclic coordinated gold-silver type II cluster optical waveguide material I according to Example 1 of the present invention;

[0022] Figure 7 The optically resolved Hochsler spectra of the multi-toothed heterocyclic coordinated gold-silver type II cluster optical waveguide material II according to Example 2 of the present invention are shown at different excitation light points and edge spacings;

[0023] Figure 8 The figure shows the ratio of the intensity of the crystal top and the main body to the distance between the top excitation point and the emission point of the multi-dentate heterocyclic coordinated gold-silver type II cluster optical waveguide material II of Example 2 of the present invention. DETAILED DESCRIPTION

[0024] The present invention provides a multi-tooth heterocyclic coordinated gold-silver type II cluster having the following structure:

[0025]

[0026] Wherein, R is H, halogen or alkyl, the halogen is fluorine, chlorine, bromine or iodine, the alkyl is an alkyl containing C1-C6 carbon atoms, preferably an alkyl containing C1-C3 carbon atoms, and R is preferably hydrogen, fluorine or methyl, more preferably fluorine.

[0027] In the present invention, the structure of the cluster is specifically one of the following structures:

[0028]

[0029] The polydentate heterocyclic coordinated gold-silver type II cluster provided by the present invention is obtained by the reaction and coordination of a polydentate heterocyclic ligand (preferably a modified thioketoxazole ligand) and a gold-silver salt. The synergistic effect of the gold and silver atoms in the cluster can enhance the luminescence performance, achieve high luminescence quantum efficiency, improve the optical waveguide performance and broaden the optical waveguide material system.

[0030] By utilizing multidentate coordination to increase ligand-metal spin-orbit coupling, the cluster's S1 and T1 states are primarily generated by metal-to-ligand charge transfer (MLCT), with the non-radiative triplet cluster-centered portion being negligible, thereby enhancing cluster emission. Simultaneously, the cluster's luminescence color can be tuned by modifying the benzene ring donor and acceptor. The multidentate heterocyclic-coordinated gold-silver-type II cluster optical waveguide material prepared by this invention can achieve a low optical loss coefficient, further improving optical waveguide performance, with an optical loss coefficient as low as 0.0100 dB·μm -1 .

[0031] The present invention also provides a method for preparing the aforementioned multidentate heterocyclic gold-silver type II clusters, which are obtained by a coordination reaction between sulfur and nitrogen atoms in the multidentate heterocyclic ligands and gold and silver salts. Specifically, the multidentate heterocyclic ligands are subjected to a coordination reaction with gold and silver salts in a solvent, followed by post-processing to obtain the multidentate heterocyclic gold-silver type II cluster optical waveguide material.

[0032] In the present invention, the multidentate heterocyclic ligand is selected from the following ligand compounds:

[0033]

[0034] R is H, halogen or alkyl, the halogen is fluorine, chlorine, bromine or iodine, the alkyl is a C1-C6 alkyl, preferably a C1-C3 alkyl, and R is preferably hydrogen, fluorine or methyl, more preferably fluorine.

[0035] In the present invention, the multidentate heterocyclic ligand is selected from one or more of R-POT, S-POT, FPOT and CH3POT;

[0036] The R-POT is:

[0037] The S-POT is:

[0038] The FPOT is:

[0039] The CH3POT is:

[0040] In the present invention, the gold and silver salts are selected from one or more of gold (dimethyl sulfide) chloride, chloroauric acid, gold chloride, tetrahydrothiophene gold chloride, silver tetrafluoroborate, silver nitrate, and silver trifluoroacetate, preferably one or more of gold (dimethyl sulfide) chloride, tetrahydrothiophene gold chloride, silver tetrafluoroborate, and silver nitrate, and more preferably gold (dimethyl sulfide) chloride and silver tetrafluoroborate.

[0041] The ratio of the polydentate heterocyclic ligand to (dimethyl sulfide) gold chloride and silver tetrafluoroborate is 1:(1.0-5.0):(1.0-5.0), preferably 1:(2.0-4.0):(1.5-4.5), and more preferably 1:(2.5-3.5):(1.7-3.0).

[0042] In the present invention, the multidentate heterocyclic ligand is prepared by reacting a modified amino alcohol compound with carbon disulfide and hydrogen peroxide.

[0043] In the present invention, the multidentate heterocyclic ligand is prepared by the following method:

[0044] Step (1) is to prepare a modified amino alcohol compound by performing a reduction reaction with iodine and a reducing agent. The molar ratio of the modified amino acid compound to iodine is 1:(1.0-1.8), preferably 1:(1.1-1.5), more preferably 1:(1.2-1.4). The molar ratio of the modified amino acid compound to the reducing agent is 1:(2.0-3.5), preferably 1:(2.1-3.3), more preferably 1:(2.2-3.0).

[0045] In step (1), the modified amino acid compound is selected from halogen-containing amino acids and alkyl amino acids, more preferably fluoro amino acids and methyl amino acids;

[0046] In step (1), the reducing agent is preferably one or more of oxalic acid, potassium borohydride, sodium borohydride, and lithium aluminum hydride, more preferably sodium borohydride;

[0047] The reaction is carried out in a solvent, preferably one or more of an ether solvent, an ester solvent, and a ketone solvent, more preferably one or more of diethyl ether, methyl ethyl ether, tetrahydrofuran, ethyl acetate, butyl acetate, methyl butyl ketone, acetone, and cyclohexanone, with tetrahydrofuran being most preferred. The molar volume ratio of the modified amino acid compound to the solvent is 1 mmol: (10.0-20.0) mL, preferably 1 mmol: (12.0-18.0) mL, and more preferably 1 mmol: (13.0-15.0) mL.

[0048] The step (1) may be specifically as follows: During the reaction process, the modified amino acid compound is first reacted with a reducing agent at 0-10°C, iodine is then added dropwise to continue the reaction, and the temperature is then raised to 75-80°C and the reaction is continued for 15-20 hours. The mixture is cooled to 20-25°C, and then an appropriate amount of methanol is added, stirred for 30-60 minutes, a 2-3M aqueous solution of NaOH is added, stirred for 2-4 hours, and an appropriate amount of deionized water and dichloromethane (DCM) are added for extraction. After the organic layer is dried, the solvent is evaporated to obtain the modified amino alcohol compound.

[0049] Step (2), reacting the modified amino alcohol compound with a base compound, carbon disulfide, and hydrogen peroxide, and adding the reactants to the reaction solution to obtain a reaction solution.

[0050] In step (2), the alkaline compound is preferably one or more of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, aluminum hydroxide, sodium bicarbonate, and ammonia water, more preferably one or more of potassium hydroxide, sodium hydroxide, sodium carbonate and potassium carbonate, and most preferably potassium hydroxide.

[0051] The reaction is carried out in a solvent, which is preferably one or more of an alcohol solvent, an ester solvent and a ketone solvent, more preferably one or more of methanol, ethanol, propanol, ethyl acetate, butyl acetate, methyl butanone, acetone and cyclohexanone, and most preferably methanol solvent.

[0052] The molar ratio of the modified amino alcohol compound to the base compound is 1:(0.3-1.2), preferably 1:(0.4-1.0), and more preferably 1:(0.5-0.8).

[0053] The molar volume ratio of the modified amino alcohol compound to carbon disulfide is 1 mmol: (0.8-1.5) mL, preferably 1 mmol: (0.9-1.4) mL, and more preferably 1 mmol: (1.1-1.3) mL.

[0054] The molar volume ratio of the modified amino alcohol compound to hydrogen peroxide is 1 mmol: (0.2-1.2) mL, preferably 1 mmol: (0.3-1.0) mL, and more preferably 1 mmol: (0.4-0.8) mL.

[0055] The molar volume ratio of the modified amino acid compound to the solvent is 1 mmol: (8.0-18.0) mL, preferably 1 mmol: (9.0-17.0) mL, and more preferably 1 mmol: (10.0-15.0) mL.

[0056] Specifically, step (2) may include: during the reaction, first reacting the modified amino alcohol compound with the base compound, then adding carbon disulfide dropwise at 0-10°C, then heating to 70-80°C and continuing the reaction for 20-50 minutes. Cooling to 0-10°C, then adding hydrogen peroxide dropwise, then heating to 70-80°C and continuing the reaction for 15-20 hours. Cooling to 20-25°C to obtain a reaction solution.

[0057] Step (3) post-treating the reaction solution to obtain a polydentate heterocyclic ligand. Specifically, the following steps can be performed: adding appropriate amounts of deionized water and dichloromethane (DCM) to the reaction solution in step 2 for extraction. After drying the organic layer, the solvent is evaporated to obtain a polydentate heterocyclic ligand.

[0058] In the present invention, the coordination reaction is carried out in a solvent, and the solvent is selected from at least one of a halogenated alkane solvent, an alcohol solvent and a nitrile solvent;

[0059] The halogenated alkane solvent is preferably at least one of dichloromethane and chloroform;

[0060] The alcohol solvent is preferably at least one of methanol, ethanol and ethylene glycol;

[0061] The nitrile solvent is preferably one or more of acetonitrile and benzyl cyanide;

[0062] The solvent is more preferably one or more of dichloromethane, chloroform, methanol, ethanol, and acetonitrile;

[0063] The most preferred solvents are dichloromethane, methanol and acetonitrile.

[0064] In the coordination reaction, the molar volume ratio of the multidentate heterocyclic ligand to the solvent is 1 mmol:(3.0-12.0) mL:(1.0-10.0) mL:(1.0-10.0) mL, preferably 1 mmol:(4.0-11.0) mL:(2.0-9.0) mL:(2.0-9.0) mL, and more preferably 1 mmol:(5.0-10.0) mL:(3.0-6.0) mL:(3.0-8.0) mL.

[0065] The reaction temperature is 10-45°C, preferably 15-40°C, more preferably 20-30°C; the reaction time is 6-21 hours, preferably 8-18 hours, more preferably 10-15 hours.

[0066] The post-treatment includes solvent selection and column purification. The column purification is to use a mixed solvent of dichloromethane and petroleum ether as a mobile phase to purify the product by a chromatographic column.

[0067] The coordination reaction can be specifically:

[0068] The multidentate heteroatom ligand is reacted with (tht)AuCl and AgBF4 in a mixed solvent of dichloromethane, acetonitrile and methanol at 20-25°C with stirring for 10-15 hours, and then the product is spin-dried and purified by column chromatography using dichloromethane (DCM) and petroleum ether (PE) as eluents to obtain a multidentate heteroatom-coordinated gold-silver type II cluster optical waveguide material.

[0069] The application of the multi-dentate heterocyclic coordinated gold-silver type II cluster provided by the present invention in optical waveguide materials, which has modified thioketoxazole ligands with donors and acceptors, effectively improves the luminescence quantum efficiency of the cluster, further improves the optical waveguide performance and broadens the optical waveguide material system. The preparation method is fast and simple, which is conducive to promotion.

[0070] The technical solution of the present invention is described in detail below with reference to specific embodiments, as follows:

[0071] Example 1

[0072] Dissolve 10 mmol of R-2-amino-2-phenylacetic acid and 22 mmol of sodium borohydride in 130 mL of dry tetrahydrofuran. Dissolve 13 mmol of iodine in 10 mL of dry tetrahydrofuran and add dropwise at a rate of 2 s / d at 0-10°C. After the addition is complete, raise the temperature to 78°C and continue the reaction for 18 hours. Cool to 25°C, then add an appropriate amount of methanol and stir for 40 minutes. Add 2M aqueous NaOH solution and stir for 3 hours. Extract with appropriate amounts of deionized water and dichloromethane (DCM). After drying the organic layer, evaporate the solvent to yield R-2-amino-2-phenylethylthio-1-ol.

[0073] Dissolve 10 mmol of the R-2-amino-2-phenylethylthio-1-ol prepared above in 120 mL of methanol. Add 6 mmol of potassium hydroxide and cool to 0-10°C. Then, add 12 mL of carbon disulfide dropwise at a rate of 2 s / d. After the addition is complete, heat the mixture to 78°C and continue the reaction for 40 min. Then, add 5 mL of hydrogen peroxide dropwise at a rate of 2 s / d at 0-10°C. Then, heat the mixture to 78°C and continue the reaction for 16 h. Cool the mixture to 20°C to obtain a reaction solution.

[0074] To the reaction solution in step 2, appropriate amounts of deionized water and dichloromethane (DCM) were added for extraction. After the organic layer was dried, the solvent was evaporated to obtain the multidentate heterocyclic ligand R-POT.

[0075] 1 mmol of multidentate heteroatom ligand R-POT was reacted with 3 mmol of gold(dimethyl sulfide) chloride and 2.0 mmol of silver tetrafluoroborate in 6 mL of dichloromethane, 4 mL of acetonitrile and 5 mL of methanol mixed solvent at 25°C with stirring for 12 hours. The mixture was then spin-dried and purified by column chromatography using dichloromethane (DCM) and petroleum ether (PE) as eluents to obtain cluster Au2Ag2(R-POT)4, which is multidentate heterocyclic coordinated gold-silver type II cluster optical waveguide material I.

[0076] The multifunctional modified Au2Ag2(R-POT)4 prepared in this experiment was tested by nuclear magnetic resonance, and the test results are as follows:

[0077] 1 H NMR (TMS, CDCl3, 400MHz):=4.49-7.66 (m, 8H).

[0078] The prepared multifunctional modified Au2Ag2(R-POT)4 was tested by mass spectrometry, and the time-of-flight mass spectrum data were: 1323.9(100)[M + ].

[0079] The elemental analysis of the prepared multifunctional modified Au2Ag2(R-POT)4 was carried out, and the test data were:

[0080] Molecular formula C 36 H 36 N4O4S4Au2Ag2;

[0081] Theoretical value:

[0082] C, 30.59; H, 2.74; Au, 29.69; Ag, 16.26; O, 4.82; N, 4.22; O, 4.82; S, 9.67.

[0083] The UV fluorescence spectrum and fluorescence spectrum of the multidentate heteroatom coordinated gold-silver type II cluster optical waveguide material Ⅰ are shown in the following figure: Figure 1 shown.

[0084] In this experiment, the light-resolved Hochsler spectra of the multidentate heteroatom-coordinated gold-silver type II cluster optical waveguide material Ⅰ with different excitation light spots and edge spacings are shown in the figure below. Figure 5 shown.

[0085] The experimental results show the ratio of the intensity of the top and the main body of the crystal of the multidentate heteroatom coordinated gold-silver type II cluster optical waveguide material I to the distance between the top excitation point and the emission point. Figure 6 As shown, its optical loss coefficient is 0.0100dB·μm -1 .

[0086] Thermogravimetric analysis of the multidentate heteroatom coordinated gold-silver type II cluster optical waveguide material I showed that its pyrolysis temperature was 226℃.

[0087] Example 2

[0088] Dissolve 10 mmol of S-2-amino-2-phenylacetic acid and 25 mmol of sodium borohydride in 130 mL of dry tetrahydrofuran. Dissolve 12 mmol of iodine in 10 mL of dry tetrahydrofuran and add dropwise at a rate of 2 s / d at 0-10°C. After the addition is complete, raise the temperature to 78°C and continue the reaction for 18 hours. Cool to 25°C, then add an appropriate amount of methanol and stir for 40 minutes. Add 2M aqueous NaOH solution and stir for 3 hours. Extract with appropriate amounts of deionized water and dichloromethane (DCM). After drying the organic layer, evaporate the solvent to yield S-2-amino-2-phenylethylthio-1-ol.

[0089] Dissolve 10 mmol of the prepared S-2-amino-2-phenylethylthio-1-ol in 120 mL of methanol. Add 5 mmol of potassium hydroxide and cool to 0-10°C. Then, add 12 mL of carbon disulfide dropwise at a rate of 2 s / d. After the addition is complete, heat the mixture to 78°C and continue the reaction for 40 min. Then, add 5 mL of hydrogen peroxide dropwise at a rate of 2 s / d at 0-10°C. Then, heat the mixture to 78°C and continue the reaction for 16 h. Cool the mixture to 20°C to obtain a reaction solution.

[0090] To the reaction solution in step 2, appropriate amounts of deionized water and dichloromethane (DCM) were added for extraction. After the organic layer was dried, the solvent was evaporated to obtain the multidentate heterocyclic ligand S-POT.

[0091] 1 mmol of the multidentate heteroatom ligand S-POT was reacted with 3.1 mmol of gold (dimethyl sulfide) chloride and 2.5 mmol of silver tetrafluoroborate in a mixed solvent of 6 mL of dichloromethane, 4 mL of acetonitrile and 5 mL of methanol, and stirred at 25°C for 12 hours. The reaction was then spin-dried and purified by column chromatography using dichloromethane (DCM) and petroleum ether (PE) as eluents to obtain the cluster Au2Ag2(R-POT)4, which is a multidentate heterocyclic coordinated gold-silver type II cluster optical waveguide material II.

[0092] The multifunctional modified Au2Ag2(S-POT)4 prepared in this experiment was tested by nuclear magnetic resonance, and the test results are as follows:

[0093] 1 H NMR (TMS, CDCl3, 400MHz):=4.49-7.96 (m, 8H).

[0094] The prepared multifunctional modified Au2Ag2(S-POT)4 was tested by mass spectrometry, and the time-of-flight mass spectrum data were: 1323.9(100)[M + ].

[0095] The elemental analysis of the prepared multifunctional modified Au2Ag2(S-POT)4 was carried out, and the test data were as follows:

[0096] Molecular formula C 36 H 36 N4O4S4Au2Ag2;

[0097] Theoretical value:

[0098] C, 30.59; H, 2.74; Au, 29.69; Ag, 16.26; O, 4.82; N, 4.22; O, 4.82; S, 9.67.

[0099] The UV fluorescence spectrum and fluorescence spectrum of the multidentate heteroatom coordinated gold-silver type II cluster optical waveguide material II are shown in the following figure. Figure 2 shown.

[0100] In this experiment, the light-resolved Hochsler spectra of the multidentate heteroatom-coordinated gold-silver type II cluster optical waveguide material Ⅰ with different excitation light spots and edge spacings are shown in the figure below. Figure 7 shown.

[0101] The experimental results show the ratio of the intensity of the top and the main body of the crystal of the multidentate heteroatom coordinated gold-silver type II cluster optical waveguide material I to the distance between the top excitation point and the emission point. Figure 8 As shown, the optical loss coefficient is 0.0161dB·μm -1 .

[0102] Thermogravimetric analysis of the multidentate heteroatom coordinated gold-silver type II cluster optical waveguide material II showed that its pyrolysis temperature was 230℃.

[0103] Example 3

[0104] Dissolve 10 mmol of 2-amino-2-(4-fluorophenyl)acetic acid and 30 mmol of sodium borohydride in 150 mL of dry tetrahydrofuran. Dissolve 14 mmol of iodine in 10 mL of dry tetrahydrofuran and add dropwise at a rate of 2 s / d at 0-10°C. After the addition is complete, raise the temperature to 78°C and continue the reaction for 20 hours. Cool to 25°C, then add an appropriate amount of methanol and stir for 50 minutes. Add 3M aqueous NaOH and stir for 4 hours. Extract with appropriate amounts of deionized water and dichloromethane (DCM). After drying the organic layer, evaporate the solvent to yield 2-amino-2-(4-fluorophenyl)-1-ethanol.

[0105] Dissolve 10 mmol of the above-prepared 2-amino-2-(4-fluorophenyl)-1-ethanol in 150 mL of methanol. Add 8 mmol of potassium hydroxide and cool to 0-10°C. Then, add 13 mL of carbon disulfide dropwise at a rate of 2 s / d. After the addition is complete, heat the mixture to 78°C and continue the reaction for 40 min. Then, add 6 mL of hydrogen peroxide dropwise at a rate of 2 s / d at 0-10°C. Then, heat the mixture to 78°C and continue the reaction for 16 h. Cool the mixture to 20°C to obtain a reaction solution.

[0106] To the reaction solution in step 2, appropriate amounts of deionized water and dichloromethane (DCM) were added for extraction. After the organic layer was dried, the solvent was evaporated to obtain the multidentate heterocyclic ligand FPOT.

[0107] 1 mmol of the multidentate heteroatom ligand FPOT was reacted with 3.5 mmol of gold(dimethyl sulfide) chloride and 3.0 mmol of silver tetrafluoroborate in a mixed solvent of 5 mL of dichloromethane, 5 mL of acetonitrile and 4 mL of methanol, and stirred at 25°C for 12 hours. The mixture was then spin-dried and purified by column chromatography using dichloromethane (DCM) and petroleum ether (PE) as eluents to obtain the cluster Au2Ag2(FPOT)4, which is a multidentate heterocyclic coordinated gold-silver type II cluster optical waveguide material III.

[0108] The multifunctional modified Au2Ag2(FPOT)4 prepared in this experiment was tested by nuclear magnetic resonance, and the test results are as follows:

[0109] 1 H NMR (TMS, CDCl3, 400MHz):=4.47-8.00 (m, 7H).

[0110] The prepared multifunctional modified Au2Ag2(FPOT)4 was tested by mass spectrometry, and the time-of-flight mass spectrum data were: 1395.9(100)[M + ].

[0111] The elemental analysis of the prepared multifunctional modified Au2Ag2(FPOT)4 was carried out, and the test data were as follows:

[0112] Molecular formula C 36 H 32 F4N4O4S4Au2Ag2;

[0113] Theoretical value:

[0114] C, 30.92; H, 2.31; Au, 28.17; Ag, 15.43; F, 5.43; N, 4.01; O, 4.58; S, 9.17.

[0115] The UV fluorescence spectrum and fluorescence spectrum of the multidentate heteroatom coordinated gold-silver type II cluster optical waveguide material III are shown in the following figure: Figure 3 shown.

[0116] Thermogravimetric analysis of the multidentate heteroatom coordinated gold-silver type II cluster optical waveguide material III showed that its pyrolysis temperature was 339℃.

[0117] Example 4

[0118] Dissolve 10 mmol of 2-amino-2-(p-tolyl)acetic acid and 25 mmol of sodium borohydride in 150 mL of dry tetrahydrofuran. Dissolve 12 mmol of iodine in 10 mL of dry tetrahydrofuran and add dropwise at a rate of 2 s / d at 0-10°C. After the addition is complete, raise the temperature to 80°C and continue the reaction for 18 hours. Cool to 25°C, then add an appropriate amount of methanol and stir for 30 minutes. Add 3M aqueous NaOH and stir for 3 hours. Extract with appropriate amounts of deionized water and dichloromethane (DCM). After drying the organic layer, evaporate the solvent to yield 2-amino-2-(p-tolyl)ethane-1-ol.

[0119] Dissolve 10 mmol of the above-prepared 2-amino-2-(p-tolyl)ethane-1-ol in 140 mL of methanol. Add 6 mmol of potassium hydroxide and cool to 0-10°C. Then, add 12 mL of carbon disulfide dropwise at a rate of 2 s / d. After the addition is complete, heat the mixture to 78°C and continue the reaction for 30 min. Then, add 7 mL of hydrogen peroxide dropwise at a rate of 2 s / d at 0-10°C. Then, heat the mixture to 78°C and continue the reaction for 15 h. Cool to 20°C to obtain a reaction solution.

[0120] To the reaction solution in step 2, appropriate amounts of deionized water and dichloromethane (DCM) were added for extraction. After the organic layer was dried, the solvent was evaporated to obtain the multidentate heterocyclic ligand CH3POT.

[0121] 1 mmol of the multidentate heteroatom ligand CH3POT was reacted with 2.5 mmol of gold(dimethyl sulfide) chloride and 1.8 mmol of silver tetrafluoroborate in a mixed solvent of 8 mL of dichloromethane, 5 mL of acetonitrile and 3 mL of methanol, and stirred at 25°C for 12 hours. The mixture was then spin-dried and purified by column chromatography using dichloromethane (DCM) and petroleum ether (PE) as eluents to obtain the cluster Au2Ag2(CH3POT)4, which is a multidentate heterocyclic coordinated gold-silver type II cluster optical waveguide material IV.

[0122] The multifunctional modified Au2Ag2(CH3POT)4 prepared in this experiment was tested by nuclear magnetic resonance, and the test results are as follows:

[0123] 1H NMR (TMS, CDCl3, 400MHz): =7.15-7.49 (m, 44H).

[0124] The prepared multifunctional modified Au2Ag2(CH3POT)4 was tested by mass spectrometry, and the time-of-flight mass spectrum data were: 1379.9(100)[M + ].

[0125] The elemental analysis of the prepared multifunctional modified Au2Ag2(CH3POT)4 was carried out, and the test data were: molecular formula C 40 H 44 N4O4S4Au2Ag2;

[0126] Theoretical values: C, 34.75; H, 3.21; Au, 15.60; Ag, 28.49; N, 4.05; O, 4.63; S, 9.27.

[0127] The ultraviolet fluorescence spectrum and fluorescence spectrum of the multidentate heteroatom coordinated gold-silver type II cluster optical waveguide material IV are shown in the following figure: Figure 4 shown.

[0128] Thermogravimetric analysis of the multidentate heteroatom coordinated gold-silver type II cluster optical waveguide material IV showed that its pyrolysis temperature was 350℃.

[0129] Research on active optical waveguide materials has primarily focused on inorganic semiconductors, polymers, polycyclic aromatic hydrocarbons, and hybrid materials. While traditional inorganic semiconductors are widely used, they also have inherent limitations, including high-temperature processing requirements, complex manufacturing techniques, and the fact that the prepared particles are sometimes too small to transmit light. While polymer materials have been tuned for optical properties through methods such as multi-component doping architectures, copolymer nanofiber engineering, or coordination polymers, the optical loss of polymer Cu-dcp has been successfully reduced to 0.08 dB·μm. -1 However, inherent challenges such as low crystallinity and difficult-to-control degree of polymerization greatly reduce the performance indicators of waveguides. Polycyclic aromatic hydrocarbon organic optical waveguide materials have achieved tunable emission and polymorphism through the development of single-component small molecules, multi-component eutectics and other systems. Although the elasticity of the crystal can be maintained through interaction, the weak force will be affected by environmental factors, resulting in limited optical waveguide performance. Hybrid materials mainly include perovskite materials and coordination materials, which are usually composed of organic ligands and transition metals or metal halides. Although hybrid materials have interactions between metals and ligands, due to the small amount of metal contained and the weak or suppressed interaction, the hybrid materials have poor stability, a single molecular configuration, and hindered charge transfer at the hybrid interface, which limits their development in optical waveguide systems.

Claims

1. A polydentate heterocyclic coordinated gold-silver type II cluster, characterized in that: Has the following structure: Wherein, R is H, halogen or alkyl, the halogen is fluorine, chlorine, bromine or iodine, the alkyl is an alkyl containing C1-C6 carbon atoms, preferably an alkyl containing C1-C3 carbon atoms, and R is preferably hydrogen, fluorine or methyl, more preferably fluorine.

2. A multi-dentate heterocyclic coordinated gold-silver type II cluster according to claim 1, characterized in that: The structure of the cluster is specifically one of the following structures:

3. The method for preparing a multi-dentate heterocyclic coordinated gold-silver type II cluster according to claim 1 or 2, characterized in that: It is obtained by coordination reaction between sulfur and nitrogen atoms in multidentate heterocyclic ligands and gold and silver salts.

4. The method for preparing a multi-toothed heterocyclic coordinated gold-silver type II cluster according to claim 1, characterized in that: The multidentate heterocyclic ligand is selected from the following ligand compounds: R is H, halogen or alkyl, the halogen is fluorine, chlorine, bromine or iodine, the alkyl is a C1-C6 alkyl, preferably a C1-C3 alkyl, and R is preferably hydrogen, fluorine or methyl, more preferably fluorine.

5. The method for preparing a multi-tooth heterocyclic coordinated gold-silver type II cluster according to claim 1, characterized in that: The multidentate heterocyclic ligand is selected from one or more of R-POT, S-POT, FPOT and CH3POT; The R-POT is: The S-POT is: The FPOT is: The CH3POT is:

6. The method for preparing a multi-dentate heterocyclic coordinated gold-silver type II cluster according to claim 1, characterized in that: The gold and silver salts are selected from one or more of gold (dimethyl sulfide) chloride, chloroauric acid, gold chloride, tetrahydrothiophene gold chloride, silver tetrafluoroborate, silver nitrate, and silver trifluoroacetate, preferably one or more of gold (dimethyl sulfide) chloride, tetrahydrothiophene gold chloride, silver tetrafluoroborate, and silver nitrate, and more preferably gold (dimethyl sulfide) chloride and silver tetrafluoroborate.

7. The method for preparing a multi-dentate heterocyclic coordinated gold-silver type II cluster according to claim 3, characterized in that: The multidentate heterocyclic ligand is prepared by reacting a modified amino alcohol compound with carbon disulfide and hydrogen peroxide.

8. The method for preparing a multi-dentate heterocyclic coordinated gold-silver type II cluster according to claim 7, characterized in that: The multidentate heterocyclic ligand is prepared by the following method: Step (1), using the modified amino acid compound to react with iodine and a reducing agent to prepare a modified amino alcohol; In step (1), the modified amino acid compound is selected from halogen-containing amino acids and alkyl amino acids, more preferably fluoro amino acids and methyl amino acids; In step (1), the reducing agent is preferably one or more of oxalic acid, potassium borohydride, sodium borohydride, and lithium aluminum hydride, more preferably sodium borohydride; The reaction is carried out in a solvent, which is preferably one or more of an ether solvent, an ester solvent and a ketone solvent, more preferably one or more of diethyl ether, methyl ethyl ether, tetrahydrofuran, ethyl acetate, butyl acetate, methyl butyl ketone, acetone and cyclohexanone, and most preferably tetrahydrofuran solvent; Step (2), reacting the modified amino alcohol compound with a base compound, carbon disulfide, and hydrogen peroxide, and adding them to the reaction solution to react to obtain a reaction solution; In step (2), the alkaline compound is preferably one or more of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, aluminum hydroxide, sodium bicarbonate, and ammonia water, more preferably one or more of potassium hydroxide, sodium hydroxide, sodium carbonate, and potassium carbonate, and most preferably potassium hydroxide; The reaction is carried out in a solvent, which is preferably one or more of an alcohol solvent, an ester solvent, and a ketone solvent, more preferably one or more of methanol, ethanol, propanol, ethyl acetate, butyl acetate, methyl butyl ketone, acetone, and cyclohexanone, and most preferably methanol solvent; Step (3), post-treating the reaction solution to obtain a multidentate heterocyclic ligand.

9. The method for preparing a multi-dentate heterocyclic coordinated gold-silver type II cluster according to claim 3, characterized in that: The coordination reaction is carried out in a solvent, and the solvent is selected from at least one of a halogenated alkane solvent, an alcohol solvent and a nitrile solvent; The halogenated alkane solvent is preferably at least one of dichloromethane and chloroform; The alcohol solvent is preferably at least one of methanol, ethanol and ethylene glycol; The nitrile solvent is preferably one or more of acetonitrile and benzyl cyanide; The solvent is more preferably one or more of dichloromethane, chloroform, methanol, ethanol, and acetonitrile; The most preferred solvents are dichloromethane, methanol and acetonitrile.

10. Use of the multidentate heterocyclic coordinated gold-silver type II cluster according to claim 1 or 2 in optical waveguide materials.

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