Photosensitive clusters, methods of synthesis and use thereof
By adding organophosphorus ligands and dibenzyl disulfide elemental ethers to a metal salt solution and combining them with NaBH4 to prepare photosensitive clusters, and then decomposing and recombining them under light using benzyl radicals, the problems of complex transformation conditions and unclear product composition in traditional methods were solved, achieving the effect of efficient preparation of new clusters.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- INNER MONGOLIA UNIVERSITY
- Filing Date
- 2026-03-24
- Publication Date
- 2026-06-12
Smart Images
Figure CN122188642A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of photosensitive materials, and more specifically, to a photosensitive cluster, its synthesis method, and its applications. Background Technology
[0002] In the field of clusters, the preparation of novel clusters is a crucial technique for the precise construction of functional metal nanoclusters (NCs) in a controlled manner. Transforming pre-prepared NCs into new materials remains a promising and efficient method.
[0003] The transformation of pre-prepared NCs into new materials typically involves physical or chemical changes under the stimulation of external factors such as light, electricity, heat, or other substances, resulting in new substances. Because this preparation method is simple, highly selective, and widely applicable, it is widely used to discover and prepare compounds that are difficult to separate or functionalize using bottom-up reduction methods.
[0004] However, traditional pre-synthesis-conversion methods also have some problems in application, such as complex conversion conditions and unclear composition of synthesized products. These problems hinder our understanding of their structure, properties, and potential applications, and also affect the preparation efficiency. Therefore, improving the composition and structure of pre-prepared photosensitive materials to enhance preparation efficiency has become a current research hotspot. Summary of the Invention
[0005] In view of this, the present invention provides a method for synthesizing photosensitive clusters and their applications.
[0006] include: An organophosphorus ligand solution and a dibenzyl disulfide elemental ether solution are added to a metal salt solution to form a first mixed solution; Add NaBH4 solution to the first mixed solution and stir for an appropriate time to obtain sufficient precipitation; After the precipitate is dissolved, it is diffused and crystallized by diethyl ether, and the resulting crystal is the photosensitive cluster.
[0007] In some embodiments of the present invention, the mass ratio of the metal salt solution, organophosphorus ligand, dibenzyl disulfide ether, and NaBH4 is 1:(0.7~1.3):(0.7~1.3):(0.7~1.3). In some embodiments of the present invention, the mass ratio of the metal salt solution, organophosphorus ligand, dibenzyl disulfide ether, and NaBH4 is 1:(0.7~1.3):(0.7~1.3):(0.7~1.3).
[0008] In some embodiments of the present invention, the synthesis method employs a one-pot synthesis.
[0009] In some embodiments of the present invention, the clusters contain benzyl groups.
[0010] In some embodiments of the present invention, the reaction temperature of the synthesis method is 5~40°C.
[0011] In some embodiments of the present invention, the solvent of the metal salt solution includes a mixed solution of acetonitrile and methanol; In some embodiments of the present invention, the solvent of the organophosphorus ligand solution includes chloroform; In some embodiments of the present invention, the solvent of the dibenzyl disulfide elemental ether solution includes a mixed solution of chloroform and acetonitrile; In some embodiments of the present invention, the solvent of the NaBH4 solution includes methanol.
[0012] Another aspect of the present invention provides the application of photosensitive clusters as described above or photosensitive clusters prepared by the synthesis method described above in photochemical self-conversion.
[0013] In some embodiments of the present invention, the photosensitive cluster solution is transformed into new clusters under illumination; wherein the wavelength of the light source is greater than or equal to 200 nanometers.
[0014] Based on the above technical solution, it can be seen that the present invention has at least one or a portion of the following advantages over the prior art: This invention introduces benzyl groups onto the surface of clusters, giving the clusters photosensitive properties in solution. Under light irradiation, these clusters can transform into new clusters with compositions and structures different from the original clusters. This preparation method can produce new, atomically precise clusters without adding other new substances, offering convenience, speed, and high efficiency. Specifically, during light irradiation, the original clusters generate benzyl radicals. This process may trigger the decomposition of the original clusters, generating various small molecular fragments. Preliminary recombination of these fragments may lead to the formation of intermediate species. These intermediate fragments further recombine, ultimately forming new clusters. The photosensitive clusters of this invention can promote the decomposition of the original clusters and the recombination of intermediate fragments while reducing external control factors, ultimately leading to cluster formation and meeting the requirements of new cluster preparation processes. (See attached figures.) Figure 1 The X-ray single-crystal diffraction pattern of the photosensitive cluster described in Embodiment 1 of the present invention; Figure 2 This is a graph showing the color change of the photosensitive cluster solution under light over time in Example 1 of the present invention. Figure 3 This is the UV-Vis absorption spectrum of the photosensitive cluster solution described in Example 1 of the present invention as a function of light over time. Figure 4This is an in-situ ESI-MS spectrum of the photosensitive cluster solution described in Example 1 of this invention, showing its change over time under illumination. Detailed embodiments are described below with reference to the embodiments to assist those skilled in the art in fully understanding the purpose, features, and effects of this invention. Furthermore, descriptions of well-known structures and techniques are omitted in the following description to avoid unnecessarily obscuring the concept of this invention. Additionally, the various embodiments and technical features provided below can be combined with each other in any manner. Specifically, this invention also provides a method for synthesizing photosensitive clusters, comprising: adding an organophosphorus ligand solution and a dibenzyl disulfide elemental ether solution to a metal salt solution to form a first mixed solution; adding a NaBH4 solution to the first mixed solution and stirring for an appropriate time to obtain sufficient precipitation; dissolving the precipitate and diffusing crystallization with diethyl ether to obtain the resulting crystal, which is the photosensitive cluster. In some embodiments of this invention, the photosensitive cluster is a cluster co-stabilized by benzyl compounds and phosphine ligands.
[0015] In some embodiments of the present invention, the mass ratio of the metal salt solution, organophosphorus ligand, dibenzyl disulfide ether, and NaBH4 is 1:(0.7~1.3):(0.7~1.3):(0.7~1.3); any mass ratio within this range is acceptable, for example, 1:0.7:(0.7~1.3):(0.7~1.3), 1:0.8:(0.7~1.3):(0.7~1.3), 1:0.9:(0.7~1.3):(0.7~1.3), 1 :1:(0.7~1.3):(0.7~1.3), 1:1.1:(0.7~1.3):(0.7~1.3), 1:1.2:(0.7~1.3):(0.7~1.3), 1:1.3:(0.7~1.3):(0.7~1.3), 1:1.3:(0.7~1.3):(0.7~1.3), 1:(0.7~1.3):0.7:(0.7~1.3), 1:0.8:0.7:(0.7~1.3), 1:(0.7 ~1.3): 0.9: (0.7~1.3), 1: (0.7~1.3): 1.0: (0.7~1.3), 1: (0.7~1.3): 1.1: (0.7~1.3), 1: (0.7~1.3): 1.2: (0.7~1.3), 1: (0.7~1.3): 1.3: (0.7~1.3), 1: (0.7~1.3): 1.3: (0.7~1.3), 1: (0.7~1.3): (0.7~1.3): 0.7, 1: ( 0.7~1.3): (0.7~1.3): 0.8, 1: (0.7~1.3): (0.7~1.3): 0.9, 1: (0.7~1.3): (0.7~1.3): 1.0, 1: (0.7~1.3): (0.7~1.3): 1.1, 1: (0.7~1.3): (0.7~1.3): 1.2, 1: (0.7~1.3): (0.7~1.3): 1.3, 1: (0.7~1.3): (0.7~1.3): 1.3.
[0016] In some embodiments of the present invention, the synthesis method employs a one-pot synthesis.
[0017] In some embodiments of the present invention, the photosensitive cluster contains benzyl groups.
[0018] In some embodiments of the present invention, the reaction temperature of the synthesis method is 5~40℃, for example, it can be 5℃, 6℃, 7℃, 8℃, 9℃, 10℃, 11℃, 12℃, 13℃, 14℃, 15℃, 16℃, 18℃, 20℃, 22℃, 24℃, 25℃, 26℃, 28℃, 30℃, 31℃, 32℃, 33℃, 34℃, 35℃, 36℃, 37℃, 38℃, 39℃, or 40℃.
[0019] In some embodiments of the present invention, the solvent of the metal salt solution includes a mixed solution of acetonitrile and methanol; In some embodiments of the present invention, the solvent of the organophosphine ligand solution includes chloroform; In some embodiments of the present invention, the solvent of the dibenzyl disulfide elemental ether solution includes a mixed solution of chloroform and acetonitrile; In some embodiments of the present invention, the solvent of the NaBH4 solution includes methanol.
[0020] Another aspect of the present invention provides the application of photosensitive clusters as described above or photosensitive clusters prepared by the synthesis method described above in photochemical self-conversion.
[0021] In some embodiments of the present invention, the photosensitive cluster solution is transformed into new clusters under illumination; wherein the wavelength of the light source is greater than or equal to 200 nanometers, for example, it can be 200 nanometers, 300 nanometers, 400 nanometers, 405 nanometers, 410 nanometers, 415 nanometers, 420 nanometers, 425 nanometers, 430 nanometers, 440 nanometers, 450 nanometers, 460 nanometers, 470 nanometers, 480 nanometers, 490 nanometers, 500 nanometers, 600 nanometers, or 650 nanometers.
[0022] In one embodiment of the present invention, a method for synthesizing photosensitive clusters is provided, comprising the following steps: a one-pot synthesis is performed, in which a metal salt is dissolved in a mixed solution of acetonitrile and methanol, and then a chloroform solution of an organophosphorus ligand and a mixed solution of chloroform and acetonitrile of dibenzyl disulfide ether are added sequentially. The organophosphorus ligand contains P and Cu... + Coordination occurs, the chalcogenide bonds in the dibenzyldiselide break, and it reacts with Cu. + Coordination was performed. Then, a freshly prepared methanol solution of NaBH4 as a reducing agent was added dropwise to the solution, resulting in a clear yellow solution.
[0023] After stirring for 30 minutes, a precipitate gradually appeared in the resulting solution. Stirring was continued for another 30 minutes, followed by centrifugation. The precipitate was dissolved in chloroform and filtered. The filtrate was then subjected to diethyl ether evaporation and diffusion followed by crystallization. After two weeks, yellow blocky crystals were finally obtained. X-ray single-crystal diffraction revealed that the crystals were metal clusters co-stabilized by benzyl compounds and phosphine ligands. The solution of these clusters could generate new clusters upon light irradiation. In this example, the clusters contained benzyl groups; the reaction temperature was 5-40℃. The application of the copper-selenium clusters prepared by the aforementioned method for synthesizing photosensitive clusters in photochemical self-transformation involves the following steps: The solution of the photosensitive clusters is exposed to light, causing the solution color to deepen. After evaporation and diffusion in diethyl ether, crystallization is performed to obtain clusters different from the original clusters. The prepared photosensitive clusters are dissolved in dichloromethane or trichloromethane solution and placed under light with a wavelength greater than 200 nm. The original clusters generate free radicals and undergo decomposition and recombination to generate new clusters.
[0024] The solvent for dissolving the clusters is dichloromethane or trichloromethane; During the photochemical self-conversion process, samples were taken at different time points under illumination. The samples taken during the photochemical self-conversion process were analyzed by in-situ ultraviolet-visible absorption spectroscopy and in-situ electrospray ionization mass spectrometry.
[0025] The technical solution of the present invention will be further illustrated below through specific embodiments. It should be noted that the specific embodiments described below are merely illustrative examples, and the scope of protection of the present invention is not limited thereto.
[0026] The chemicals and raw materials used in the following examples are all commercially available or prepared by known methods. Unless otherwise specified, all units of raw materials are by mass. Example 1
[0027] The synthesis was carried out in a one-pot process at 25 degrees Celsius. 50 mg of [Cu(MeCN)4]BF4 was weighed and dissolved in a mixed solution of acetonitrile and methanol.
[0028] Weigh 50 mg of triphenylphosphine, dissolve it in chloroform, and add it dropwise. The P and Cu in triphenylphosphine... + Coordination is performed.
[0029] Weigh 37.4 mg of dibenzyldiselenate and dissolve it in a mixed solution of chloroform and acetonitrile. The solution is then added dropwise. The Se-Se bonds in the dibenzyldiselenate break, and the solution reacts with Cu. + Coordination is performed.
[0030] Weigh 50 mg of NaBH4 and dissolve it in methanol. While stirring, add the dissolved NaBH4 dropwise to the solution to obtain a clear yellow solution.
[0031] After stirring for 30 minutes, a precipitate gradually appeared in the resulting solution. The precipitate contained pre-prepared clusters. After stirring for another 30 minutes, the solution was centrifuged. The supernatant was discarded, the precipitate was dissolved in chloroform and filtered, and the filtrate was evaporated in diethyl ether to allow for diffusion crystallization.
[0032] Yellow blocky crystals were obtained, and X-ray single-crystal diffraction analysis revealed that they were copper-selenium clusters co-stabilized by benzyl compounds and phosphine ligands (i.e., the photosensitive clusters described in this invention). Figure 1 As shown. Example 2
[0033] This embodiment uses the same method as Example 1, except that the mass of dibenzyl diselenide is adjusted to 50 mg, and the photosensitive clusters described in this invention are obtained in the same way. Example 3
[0034] This embodiment uses the same method as Example 1, except that the mass of triphenylphosphine, dibenzyl diselenide, and NaBH4 is adjusted to 35 mg, and the photosensitive clusters described in this invention are obtained in the same way. Example 4
[0035] This embodiment uses the same method as Example 1, except that the mass of triphenylphosphine, dibenzyl diselenide, and NaBH4 is adjusted to 40 mg, and the photosensitive clusters described in this invention are obtained in the same way. Example 5
[0036] This embodiment uses the same method as Example 1, except that the mass of triphenylphosphine, dibenzyl diselenide, and NaBH4 is adjusted to 45 mg, and the photosensitive clusters described in this invention are obtained in the same way. Example 6
[0037] This embodiment uses the same method as Example 1, except that the mass of triphenylphosphine, dibenzyl diselenide, and NaBH4 is adjusted to 50 mg, and the photosensitive clusters described in this invention are obtained in the same way. Example 7
[0038] This embodiment uses the same method as Example 1, except that the mass of triphenylphosphine, dibenzyl diselenide, and NaBH4 is adjusted to 55 mg, and the photosensitive clusters described in this invention are obtained in the same way. Example 8
[0039] This embodiment uses the same method as Example 1, except that the mass of triphenylphosphine, dibenzyl diselenide, and NaBH4 is adjusted to 60 mg, and the photosensitive clusters described in this invention are obtained in the same way. Example 9
[0040] This embodiment uses the same method as Example 1, except that the mass of triphenylphosphine, dibenzyl diselenide, and NaBH4 is adjusted to 65 mg, and the photosensitive clusters described in this invention are obtained in the same way. Example 10
[0041] This embodiment uses the same method as Example 1, except that the mass of triphenylphosphine, dibenzyl diselenide, and NaBH4 is adjusted to 70 mg, and the photosensitive clusters described in this invention are obtained in the same way. Example 11
[0042] This embodiment uses the same method as Example 1, except that the mass of triphenylphosphine is adjusted to 35 mg, the mass of dibenzyl diselenide is adjusted to 60 mg, and the mass of NaBH4 is adjusted to 70 mg, thus obtaining the photosensitive clusters described in this invention. Example 12
[0043] This embodiment uses the same method as Example 1, except that the mass of triphenylphosphine is adjusted to 40 mg, the mass of dibenzyldiselenide is adjusted to 55 mg, and the mass of NaBH4 is adjusted to 45 mg, thus obtaining the photosensitive clusters described in this invention. Example 13
[0044] This embodiment uses the same method as Example 1, except that the mass of triphenylphosphine is adjusted to 45 mg, the mass of dibenzyl diselenide is adjusted to 35 mg, and the mass of NaBH4 is adjusted to 55 mg, thus obtaining the photosensitive clusters described in this invention. Example 14
[0045] This embodiment uses the same method as Example 1, except that the mass of triphenylphosphine is adjusted to 55 mg, the mass of dibenzyl diselenide is adjusted to 45 mg, and the mass of NaBH4 is adjusted to 35 mg, thus obtaining the photosensitive clusters described in this invention.
[0046] Application Example 1 The application experiment of the photosensitive clusters obtained in Example 1 above in photochemical self-conversion specifically includes the following steps: dissolving the obtained photosensitive clusters in dichloromethane, and irradiating them with light of wavelength 420 nm. The solution color deepens with increasing time, as shown below. Figure 2 As shown in the figure. Samples were taken at different illumination times (0 min, 5 min, 10 min, 20 min, 32 min, 36 min, 38 min, and 40 min, respectively), and crystallized after evaporation and diffusion in diethyl ether. The results were measured by in-situ UV-Vis absorption spectroscopy and in-situ ESI-MS spectroscopy, respectively. Figure 3 , Figure 4 As shown, it can be seen that the original cluster can generate free radicals under light, and then decompose and recombine to generate new clusters.
[0047] Application Example 2 The application experiment of the photosensitive clusters obtained in Example 1 above in photochemical self-conversion includes the following steps: the photosensitive clusters obtained above are dissolved in chloroform, and the solution color deepens with the extension of time under light irradiation at a wavelength of 405 nm. Samples are taken at different irradiation times (0 min, 5 min, 10 min, 20 min, 32 min, 36 min, 38 min, and 40 min, respectively), and crystallized after evaporation and diffusion in diethyl ether. The original clusters can generate free radicals under light irradiation and undergo decomposition and recombination to generate new clusters.
[0048] Application Example 3 The application experiment of the photosensitive clusters obtained in Example 1 above in photochemical self-conversion includes the following steps: the photosensitive clusters obtained above are dissolved in dichloromethane, and the solution color deepens with the extension of time under light irradiation at a wavelength of 410 nm. Samples are taken at different irradiation times (0 min, 5 min, 10 min, 20 min, 32 min, 36 min, 38 min, and 40 min, respectively), and crystallized after evaporation and diffusion in diethyl ether. The original clusters can generate free radicals under light irradiation and undergo decomposition and recombination to generate new clusters.
[0049] Application Example 4 The application experiment of the photosensitive clusters obtained in Example 1 above in photochemical self-conversion includes the following steps: the photosensitive clusters obtained above are dissolved in dichloromethane, and the solution color deepens with the extension of time under light irradiation at a wavelength of 450 nm. Samples are taken at different irradiation times (5 min, 10 min, 20 min, 32 min, 36 min, 38 min, and 40 min, respectively), and crystallized after evaporation and diffusion in diethyl ether. In-situ ultraviolet-visible absorption spectroscopy and in-situ ESI-MS spectroscopy tests show that the original clusters can generate free radicals under light irradiation and undergo decomposition and recombination to generate new clusters.
[0050] Application Example 5 The application experiment of the photosensitive clusters obtained in Example 1 above in photochemical self-transformation includes the following steps: the photosensitive clusters obtained above are dissolved in dichloromethane, and the solution color deepens with the extension of time under light irradiation at a wavelength of 500 nm. Samples are taken at different irradiation times (0 min, 5 min, 10 min, 20 min, 32 min, 36 min, 38 min, and 40 min, respectively), and crystallized after evaporation and diffusion in diethyl ether. The original clusters can generate free radicals under light irradiation and undergo decomposition and recombination to generate new clusters.
[0051] It should be noted that although the present invention has been shown and described with reference to specific exemplary embodiments, those skilled in the art should understand that the present invention is not limited to the above embodiments. Any modifications or variations to the present invention that do not depart from the spirit and scope of the present invention are also included in the present invention if such modifications and variations fall within the scope of the claims and equivalent technologies of the present invention.
[0052] In particular, without departing from the spirit and teachings of this invention, the features described in the various embodiments and / or claims of this invention can be combined and / or combined in various ways, even if such combinations or combinations are not expressly described in this invention. All such combinations and / or combinations are within the scope of protection of this invention. Therefore, the scope of this invention should be determined not only by the appended claims but also by their equivalents.
Claims
1. A method for synthesizing photosensitive clusters, comprising: An organophosphorus ligand solution and a dibenzyl disulfide elemental ether solution are added to a metal salt solution to form a first mixed solution. NaBH4 solution is added to the first mixed solution and the mixture is stirred until no more precipitate is formed. After the precipitate is dissolved, it is diffused and crystallized by diethyl ether, and the resulting crystal is the photosensitive cluster.
2. The synthesis method according to claim 2, characterized in that, The mass ratio of the metal salt solution, organophosphorus ligand, dibenzyl disulfide ether, and NaBH4 is 1:(0.7~1.3):(0.7~1.3):(0.7~1.3).
3. The metal salt solutions include chloroauric acid trihydrate solution, gold acetate solution, silver nitrate solution, silver trifluoroacetate solution, silver perchlorate solution, copper chloride solution, cuprous chloride solution, copper sulfate solution, copper nitrate solution, ketone acetate solution, copper perchlorate solution, copper tetrafluoroborate tetraacetonitrile solution, chloroplatinic acid solution, palladium chloride solution, sodium chloropalladate solution, cobalt acetylacetonate, nickel acetylacetonate, and other acetylacetonate metal salt solutions, etc. The organophosphorus ligands include monodentate phosphine ligands such as triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, tri(o-methylphenyl)phosphine, and trimethylphosphine; bidentate phosphine ligands such as 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,1'-bis(diphenylphosphine)ferrocene, and chiral bidentate phosphine; sterically hindered and electron-rich phosphine ligands such as tri(2-furanyl)phosphine, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, and tris(2,4-di-tert-butylphenyl)phosphite; and water-soluble phosphine ligands such as tris(m-sodium sulfonate phenyl)phosphine. The dibenzyl disulfide elemental ethers include dibenzyl diselenide, dibenzyl disulfide, dibenzyl ditelluride, etc.
4. The synthesis method according to claim 2, characterized in that, The mass ratio of the metal salt solution, organophosphorus ligand, dibenzyl disulfide ether, and NaBH4 is 1:(0.7~1.3):(0.7~1.3):(0.7~1.3).
5. The synthesis method according to claim 2, characterized in that, The synthesis method described herein employs a one-pot synthesis process.
6. The synthesis method according to claim 2, characterized in that, The cluster contains benzyl groups.
7. The synthesis method according to claim 2, characterized in that, The reaction temperature of the synthesis method is 5~40℃.
8. The synthesis method according to claim 2, characterized in that, The solvent for the metal salt solution includes a mixed solution of acetonitrile and methanol; The solvent for the organophosphorus ligand solution includes chloroform; The solvent of the dibenzyl disulfide elemental ether solution includes a mixed solution of chloroform and acetonitrile; The solvent for the NaBH4 solution includes methanol.
9. The application of the photosensitive cluster as described in claim 1 or the photosensitive cluster prepared by the synthesis method described in any one of claims 2 to 8 in photochemical self-conversion.
10. The application according to claim 9, characterized in that, The photosensitive cluster solution transforms into new clusters under light irradiation; The wavelength of the light source is greater than or equal to 200 nanometers.