CN114957310A - Trisilyl polycarboxylic organic silicon compound and synthesis method and application thereof - Google Patents
Trisilyl polycarboxylic organic silicon compound and synthesis method and application thereof Download PDFInfo
- Publication number
- CN114957310A CN114957310A CN202210597054.5A CN202210597054A CN114957310A CN 114957310 A CN114957310 A CN 114957310A CN 202210597054 A CN202210597054 A CN 202210597054A CN 114957310 A CN114957310 A CN 114957310A
- Authority
- CN
- China
- Prior art keywords
- organosilicon compound
- temperature
- reaction
- trisilyl
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000003377 silicon compounds Chemical class 0.000 title claims abstract description 45
- 238000001308 synthesis method Methods 0.000 title abstract description 12
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 116
- 239000002253 acid Substances 0.000 claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 238000004729 solvothermal method Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 73
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- 238000006138 lithiation reaction Methods 0.000 claims description 48
- 239000002904 solvent Substances 0.000 claims description 44
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 43
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- 239000000376 reactant Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 230000002194 synthesizing effect Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical group BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 claims description 6
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical group [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 6
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical group BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- DOMWJSXWPFXSMX-UHFFFAOYSA-N 1-bromo-4-(4-bromo-2-iodo-5-methoxyphenyl)-5-iodo-2-methoxybenzene Chemical group C1=C(Br)C(OC)=CC(C=2C(=CC(Br)=C(OC)C=2)I)=C1I DOMWJSXWPFXSMX-UHFFFAOYSA-N 0.000 claims description 4
- FTDZECHQBVIHKZ-UHFFFAOYSA-N 5,5-dibromo-2-phenylcyclohexa-1,3-diene Chemical group C1=CC(Br)(Br)CC=C1C1=CC=CC=C1 FTDZECHQBVIHKZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- VJIZAVQYTPKHHA-UHFFFAOYSA-N 1,3-dibromo-5-(4-iodophenyl)benzene Chemical group BrC1=CC(=CC(Br)=C1)C1=CC=C(I)C=C1 VJIZAVQYTPKHHA-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910008045 Si-Si Inorganic materials 0.000 abstract description 7
- 229910006411 Si—Si Inorganic materials 0.000 abstract description 7
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 150000000000 tetracarboxylic acids Chemical group 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- 239000000543 intermediate Substances 0.000 description 37
- 238000001228 spectrum Methods 0.000 description 34
- 239000000243 solution Substances 0.000 description 33
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 23
- 238000005481 NMR spectroscopy Methods 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 21
- 239000013078 crystal Substances 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 18
- 239000010703 silicon Substances 0.000 description 18
- 239000012074 organic phase Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 11
- 239000012300 argon atmosphere Substances 0.000 description 11
- 239000003480 eluent Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- 239000003446 ligand Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 10
- 239000012043 crude product Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000001994 activation Methods 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 229910019443 NaSi Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005424 photoluminescence Methods 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- -1 (3-bromobenzene) -1,1,1,3,3, 3-hexamethyltrisilane Chemical compound 0.000 description 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000013183 functionalized metal-organic framework Substances 0.000 description 1
- UQWQCMSYGMAGKF-UHFFFAOYSA-N hexane;lithium Chemical compound [Li].CCCCCC UQWQCMSYGMAGKF-UHFFFAOYSA-N 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
-
- 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
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention provides a trisilicon-based polycarboxylic acid organic silicon compound, a synthesis method and application thereof, wherein the trisilicon-based polycarboxylic acid organic silicon compound is any one of an organic silicon compound mMTSA, an organic silicon compound pMLSA, an organic silicon compound STSA, an organic silicon compound STSDA, an organic silicon compound TSDA and an organic silicon compound TLDA, is a trisilicon-based functional group organic silicon compound with Si-Si bonds and aromatic groups, and also has a di-or tetracarboxylic acid structure. The invention also relates to the trisilicon polycarboxylic organosilicon compound and the metal salt Zn (NO) 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·5H 2 O、Cd(NO 3 ) 2 ·4H 2 O and In (NO) 3 ) 2 ·6H 2 And O adopts a solvothermal method to prepare SiMOFs. Compared with the prior artThe trisilyl polycarboxylic organosilicon compound provided by the invention has more excellent fluorescence property, hydrophobicity and coordination participation capability, can improve the thermal stability, hydrophobicity and fluorescence property of SiMOFs when being applied to the preparation of SiMOFs, and has an expanded application range in the preparation of SiMOFs due to the polycarboxylic acid structure.
Description
Technical Field
The invention belongs to the field of organic silicon chemistry and coordination chemistry, relates to an organic silicon compound, and particularly relates to a trisilicon-based polycarboxylic organic silicon compound and a synthesis method and application thereof.
Background
In recent years, with the gradual highlighting of the advantages of Metal Organic Frameworks (MOFs) and the development of research on their wide application, the preparation of synthetic functionalized MOFs has become a hot spot for the development of materials with novel structure and good functions. Organic silicon compounds are widely concerned due to the characteristics of being not easy to damage, non-toxic, good in biocompatibility, high in thermal stability and the like, and have wide application in materials and fine chemicals, so that more and more organic silicon compound-based MOFs (SiMOFs) are designed and synthesized and are applied to the aspects of gas adsorption, photoelectricity, catalysis, fluorescent materials and the like. At present, many organosilicon compounds are designed, synthesized and reported as coordination units of the SiMOFs materials, and common organosilicon ligands used for preparing SiMOFs framework materials in related documents can be divided into bidentate, tridentate and tetradentate ligands according to the coordination number. The multidentate organosilicon ligand is synthesized and is characterized in detail earlier than a bidentate organosilicon ligand, and reports on the performance of the multidentate ligand SiMOFs are the most, mainly because the stable porous structure is easier to generate due to the coordination symmetry and the multi-point coordination characteristics of the multidentate ligand.
Although more than ten kinds of organosilicon compound ligands have been synthesized and reported to be used for preparing the SimoFs material, the Si element in the reported related ligands is only used as a connection center, and few organosilicon compounds with the Si element as a central functional group are reported to be synthesized, so that most of the prepared SiMOFs materials only have simple framework properties and metal cluster center properties.
Disclosure of Invention
By combining the essential characteristics of the organic silicon compound and the advantages of the MOFs, the advantages of the organic silicon compound can be exerted, and the performance and the application of the MOFs material can be expanded. Furthermore, ligands for the preparation of SiMOFs need to coordinate to the metal, and therefore modification of the ligands to the carboxylic acid structure is essential. The design and synthesis of polycarboxylic acid ligands with organosilicon functional groups are fundamental means for developing SiMOFs with novel structural characteristics and good performance.
In addition, sigma (Si-Si) orbitals and aromatic pi orbitals existSince an organosilicon compound having a Si — Si bond and an aromatic group has characteristics of Photoluminescence (PL), electron transport, and nonlinear optics (NLO), a σ -pi conjugated fluorescent molecular system composed of a σ (Si — Si) inserted into two pi systems has been attracting attention in recent years by many researchers. In addition, the luminescent property of the Si-Si bond can be greatly changed due to changes of the torsion angle, the fracture, the reaction and the like of the Si-Si bond, and the Si-Si bond is fractured under ultraviolet light and has good photoresponse property. Therefore, synthesizing organosilicon compounds with Si-Si bonds and aromatic groups and synthesizing SiMOFs based on the organosilicon compounds is an important strategy for preparing SiMOFs with high stability, photoluminescence and specific fluorescence. Further, Si-TMS (TMS ═ Si (CH) 3 ) 3 ) The bond has super-hydrophobicity, and the synthesis of the organic silicon compound with the Si-TMS bond and the synthesis of SiMOFs based on the organic silicon compound are one of the means for preparing the super-hydrophobic material.
In order to solve the problems in the prior art, the invention provides a trisilyl polycarboxylic acid organic silicon compound and a synthesis method and application thereof.
The specific technical scheme of the invention is as follows:
the invention provides a trisilicon-based polycarboxylic organic silicon compound, which is characterized in that the trisilicon-based polycarboxylic organic silicon compound is any one of an organic silicon compound mMTSA, an organic silicon compound pMLSA, an organic silicon compound STSA, an organic silicon compound STSDA, an organic silicon compound TSDA and an organic silicon compound TLDA, wherein the structural formulas of the organic silicon compound mMTSA, the organic silicon compound pMLSA, the organic silicon compound STSA, the organic silicon compound STSDA, the organic silicon compound TSDA and the organic silicon compound TLDA are respectively shown as the following formulas I to VI:
the invention also provides a synthesis method of the trisilicon-based polycarboxylic organic silicon compound, which is characterized by comprising the following steps: step S1, adding n-solvent to the first solvent solution of the reactants at a first temperature that is anhydrous and oxygen-freeButyl lithium n-hexane solution, the reaction system is used for carrying out the first lithiation reaction at the second temperature, and after the first lithiation reaction is finished, the solution is dropwise added at the first Temperature (TMS) 2 SiCl 2 And (4) continuing the reaction, naturally heating to room temperature after the reaction is finished, and continuing the reaction overnight. Quenching the reaction system by using a saturated ammonium chloride aqueous solution after the reaction is finished, removing an organic solvent, extracting, washing, drying, concentrating and purifying to obtain an intermediate; step S2, adding an n-hexane solution of a lithium reagent into the second solvent solution of the intermediate at a third temperature which is anhydrous and anaerobic, carrying out a second lithiation reaction in the reaction system at the third temperature, and introducing dry CO at the third reaction temperature after the second lithiation reaction is finished 2 And (4) reacting, naturally heating to room temperature or heating to continue stirring for reaction after the reaction is finished. After the reaction is finished, quenching the reaction system by using a dilute hydrochloric acid solution, adjusting the pH value to acidity, extracting, washing, drying, concentrating and purifying to obtain the trisilicon-based polycarboxylic organosilicon compound.
The synthesis method of the trisilicon-based polycarboxylic acid organic silicon compound provided by the invention also has the technical characteristics that the trisilicon-based polycarboxylic acid organic silicon compound is an organic silicon compound mMTSA, the first temperature in the step S1 is-78 ℃, the reactant is m-dibromobenzene, the first solvent is tetrahydrofuran, the second temperature is-48 ℃, the time of the first lithiation reaction is 1h, and the intermediate is mMTSA-Br; in the step S2, the third temperature is-78 ℃, the second solvent is tetrahydrofuran, the lithium reagent is n-butyllithium, and the time of the second lithiation reaction is 2 hours.
The synthesis method of the trisilyl polycarboxylic acid organosilicon compound provided by the invention is also characterized in that the trisilyl polycarboxylic acid organosilicon compound is an organosilicon compound pMLSA, the first temperature in the step S1 is 0 ℃, the reactant is 4, 4-dibromo biphenyl, the first solvent is diethyl ether, the second temperature is 0 ℃, the time of the first lithiation reaction is 1.5h, and the intermediate is pMLSA-Br; in the step S2, the third temperature is-78 ℃, the second solvent is tetrahydrofuran, the lithium reagent is n-butyllithium, and the time of the second lithiation reaction is 2 hours.
The synthesis method of the trisilyl polycarboxylic acid organosilicon compound provided by the invention is also characterized in that the trisilyl polycarboxylic acid organosilicon compound is an organosilicon compound STSA, the first temperature in the step S1 is-90 ℃, the reactant is 4,4 '-dibromo-2, 2' -diiodo-5, 5 '-dimethoxy-1, 1' -biphenyl, the first solvent is tetrahydrofuran, the second temperature is-90 ℃, the time of the first lithiation reaction is 2 hours, and the intermediate is STSA-Br; in the step S2, the third temperature is-78 ℃, the second solvent is tetrahydrofuran, the lithium reagent is n-butyllithium, and the time of the second lithiation reaction is 2 hours.
The synthesis method of the trisilicon-based polycarboxylic acid organosilicon compound provided by the invention also has the technical characteristics that the trisilicon-based polycarboxylic acid organosilicon compound is an organosilicon compound STSDA, the first temperature in the step S1 is-78 ℃, the reactant is 1,3,5 tribromobenzene, the first solvent is diethyl ether, the second temperature is-78 ℃, the time of the first lithiation reaction is 2h, and the intermediate is TSDA-Br; in the step S2, the third temperature is-78 ℃, the second solvent is tetrahydrofuran, the lithium reagent is n-butyllithium, and the time of the second lithiation reaction is 2 hours.
The synthesis method of the trisilicon-based polycarboxylic acid organic silicon compound provided by the invention also has the technical characteristics that the trisilicon-based polycarboxylic acid organic silicon compound is an organic silicon compound TSDA, the first temperature in the step S1 is-78 ℃, the reactant is 1,3,5 tribromobenzene, the first solvent is diethyl ether, the second temperature is-78 ℃, the time of the first lithiation reaction is 2h, and the intermediate is TSDA-Br; in the step S2, the third temperature is-78 ℃, the second solvent is tetrahydrofuran, the lithium reagent is tert-butyl lithium, and the time of the second lithiation reaction is 2 hours.
The synthesis method of the trisilyl polycarboxylic acid organosilicon compound provided by the invention is also characterized in that the trisilyl polycarboxylic acid organosilicon compound is an organosilicon compound TLDA, the first temperature in step S1 is-78 ℃, the reactant is 3, 5-dibromo-4 '-iodine-1, 1' -biphenyl, the first solvent is diethyl ether, the second temperature is-78 ℃, the time of the first lithiation reaction is 2 hours, and the intermediate is TLDA-Br; in the step S2, the third temperature is-78 ℃, the second solvent is tetrahydrofuran, the lithium reagent is tert-butyl lithium, and the time of the second lithiation reaction is 2 hours.
The invention also provides application of the tri-silicon-based polycarboxylic organic silicon compound in preparation of SiMOFs, which is characterized in that the tri-silicon-based polycarboxylic organic silicon compound and metal salt are prepared into the SiMOFs by adopting a solvothermal method.
The application of the trisilyl polycarboxylic acid organosilicon compound in the preparation of SiMOFs can also have the technical characteristics that metal salt is Zn (NO) 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·5H 2 O、Cd(NO 3 ) 2 ·4H 2 O and In (NO) 3 ) 2 ·6H 2 And O, the solvothermal temperature is 60-100 ℃, and the time is 20-72 hours.
Action and Effect of the invention
Because the invention synthesizes the organosilicon compound with the tri-silicon-based functional group of Si-Si bond and aromatic group through two lithiation reactions, and the organosilicon compound also has a di-or tetracarboxylic acid structure, compared with the prior art, the tri-silicon-based polycarboxylic acid organosilicon compound provided by the invention has excellent fluorescence property, hydrophobicity and coordination participation capability, and can improve the thermal stability, hydrophobicity and fluorescence property of SiMOFs when being applied to the preparation of SiMOFs, and the polycarboxylic acid structure of the tri-silicon-based polycarboxylic acid organosilicon compound enlarges the application range of the tri-silicon-based polycarboxylic acid organosilicon compound in the preparation of SiMOFs. Based on the trisilyl polycarboxylic organosilicon compound, SiMOFs with novel structure, excellent property and high stability can be developed.
Drawings
FIG. 1 is a structural formula of an organosilicon compound according to an embodiment of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of intermediate mMTSA-Br in example 1 of the present invention;
FIG. 3 is a nuclear magnetic carbon spectrum of an intermediate mMTSA-Br in example 1 of the present invention;
FIG. 4 is a nuclear magnetic silicon spectrum of an intermediate mMTSA-Br in example 1 of the present invention;
FIG. 5 is a nuclear magnetic hydrogen spectrum of organosilicon compound mMTSA in example 1 of the present invention;
FIG. 6 is a nuclear magnetic carbon spectrum of organosilicon compound mMTSA in example 1 of the present invention;
FIG. 7 is a nuclear magnetic silicon spectrum of organosilicon compound mMTSA in example 1 of the present invention;
FIG. 8 is a nuclear magnetic hydrogen spectrum of an intermediate STSA-Br in example 3 of the present invention;
FIG. 9 is a nuclear magnetic carbon spectrum of the intermediate STSA-Br of example 3 of the present invention;
FIG. 10 is a nuclear magnetic silicon spectrum of the intermediate STSA-Br of example 3 of the present invention;
FIG. 11 is a nuclear magnetic hydrogen spectrum of intermediate TSDA-Br in example 4 of the present invention;
FIG. 12 is a nuclear magnetic carbon spectrum of intermediate TSDA-Br in example 4 of the present invention;
FIG. 13 is a nuclear magnetic silicon spectrum of intermediate TSDA-Br of example 4 of the present invention;
FIG. 14 is a nuclear magnetic hydrogen spectrum of an organosilicon compound STSDA in example 4 of the present invention;
FIG. 15 is a nuclear magnetic carbon spectrum of organosilicon compound STSDA in example 4 of the present invention;
FIG. 16 is a nuclear magnetic hydrogen spectrum of an organosilicon compound TSDA in example 5 of the present invention;
FIG. 17 is a nuclear magnetic carbon spectrum of an organosilicon compound TSDA in example 5 of the present invention;
FIG. 18 is a nuclear magnetic silicon spectrum of an organosilicon compound TSDA in example 5 of the present invention;
FIG. 19 is a schematic representation of the crystal structure and stacking of organosilicon compound STSDA in example 4 of the present invention;
FIG. 20 is a schematic representation of the crystal structure of SiMOF-1 made from an example-based trisilyl polycarboxylic acid organosilicon compound of the present invention;
FIG. 21 is a schematic representation of the crystal structure of SiMOF-3 produced from an example-based trisilylpolycarboxylic acid organosilicon compound of the present invention;
FIG. 22 is a schematic representation of the crystal structure of SiMOF-4 made from an example-based trisilylpolycarboxylic acid organosilicon compound of the present invention;
FIG. 23 is a schematic representation of the topology of SiMOF-5 made from an example trisilyl polycarboxylic acid organosilicon compound;
FIG. 24 is a schematic representation of the topology of SiMOF-6 made from an example trisilylpolycarboxylic acid organosilicon compound;
FIG. 25 is a powder X-ray diffraction contrast plot of SiMOF-1 prepared based on the trisilylpolycarboxylic acid organosilicon compounds of the examples;
FIG. 26 is a thermogravimetric plot of SiMOF-1 prepared based on the trisilylpolycarboxylic acid organosilicon compounds of the examples;
FIG. 27 is a graph of the fluorescence of SiMOF-1 made based on the trisilylpolycarboxylic acid organosilicon compounds of the examples.
Detailed Description
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art.
The reagents used in the following examples are commercially available and the experimental procedures and experimental conditions not specified are those conventional in the art.
The invention provides a method for synthesizing a trisilyl polycarboxylic acid organic silicon compound, which comprises the following steps:
step S1, adding n-hexane solution of n-butyllithium into the first solvent solution of the reactant at a first temperature without water and oxygen, carrying out a first lithiation reaction at a second temperature in the reaction system, and dropwise adding (TMS) at the first temperature after the first lithiation reaction is finished 2 SiCl 2 And (4) continuing the reaction, naturally heating to room temperature after the reaction is finished, and continuing the reaction overnight. Quenching the reaction system by using a saturated ammonium chloride aqueous solution after the reaction is finished, removing an organic solvent, extracting, washing, drying, concentrating and purifying to obtain an intermediate;
step S2, adding an n-hexane solution of a lithium reagent into the second solvent solution of the intermediate at a third temperature which is anhydrous and anaerobic, carrying out a second lithiation reaction in the reaction system at the third temperature, and introducing dry CO at the third reaction temperature after the second lithiation reaction is finished 2 And (4) reacting, naturally heating to room temperature or heating to continue stirring for reaction after the reaction is finished. After the reaction is finished, the reaction system is quenched by dilute hydrochloric acid solution, the pH value is adjusted to acidity, and trisilicon is obtained by extraction, washing, drying, concentration and purificationA polycarboxylic organosilicon compound.
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings.
< example 1>
This example provides a method for synthesizing a trisilyl polycarboxylic acid organosilicon compound mtsa, comprising the steps of:
step S1, weighing the reactant m-dibromobenzene (12.0g,50.8mmol), adding the reactant m-dibromobenzene into a 250mL double-mouth bottle with a stirrer under the argon atmosphere, wherein one mouth of the double-mouth bottle is connected with a constant pressure dropping funnel. Adding 150mL of anhydrous tetrahydrofuran (namely a first solvent) into the double-mouth bottle, stirring to dissolve m-dibromobenzene, cooling the temperature to-78 ℃ (namely the first temperature), dropwise adding n-hexane solution of n-butyllithium (1.6mol/L and 38.1mL), and naturally heating the reaction system to-48 ℃ (namely the second temperature) and keeping the temperature to carry out the first lithiation reaction for 1 h. Cooling to-78 deg.C, and slowly adding dropwise (TMS) 2 SiCl 2 (6.2mL,25.4mmol) was added to the reaction and the reaction was continued at-78 deg.C for 2h, then allowed to warm to room temperature naturally overnight. After the reaction is finished, a saturated ammonium chloride aqueous solution is dripped to quench a reaction system, then a rotary evaporator is used for removing an organic solvent, dichloromethane is used for extracting the residual water phase for 3 times, an organic phase is collected, a saturated NaCl aqueous solution is washed, anhydrous magnesium sulfate is dried and filtered, and after the filtrate is dried, a crude product mMTSA-Br (2, 2-bis (3-bromobenzene) -1,1,1,3,3, 3-hexamethyltrisilane) is obtained, the compound is purified by column chromatography, normal hexane is used as an eluent, and a pure intermediate mMTSA-Br (7.8g,16.0mmol) can be obtained, the yield is 63.1%, and the structure is as follows:
step S2, weighing mMTSA-Br (4.9g,10.0mmol), adding into a 250mL double-neck bottle under argon atmosphere, adding 120mL of anhydrous tetrahydrofuran (namely a second solvent), cooling to-78 ℃ (namely a third temperature), dropwise adding n-hexane solution of n-butyllithium (2.5mol/L,4.8mL), keeping the temperature, and carrying out a second lithiation reaction for 2 h. HoldingCO dried by concentrated sulfuric acid is introduced into the system at the temperature of minus 78 DEG C 2 And (5) naturally heating the gas for 1h to room temperature, and continuously stirring and reacting for 5 h. After the reaction, the reaction system was quenched with 1M diluted hydrochloric acid solution and the pH of the system was adjusted to 3. Adding aqueous NaCl solution and extracting the aqueous phase 3 times with ethyl acetate, collecting the organic phase, washing the collected organic phase with saturated aqueous NaCl solution, drying over anhydrous magnesium sulfate and filtering, and after spin-drying the filtrate, obtaining a crude product mtsa (3,3' - (1,1,1,3, 3-hexamethyltrisilane-2, 2-diacyl) dibenzoic acid) which was eluted by column chromatography, ethyl acetate: petroleum ether: pure trisilyl polycarboxylic acid organosilicon compound mMTSA (3.2g,7.6mmol) was obtained with acetic acid ═ 10:50:1 as eluent, with 75.2% yield and the structural formula shown in formula i in fig. 1.
< example 2>
This example provides a method for synthesizing trisilyl polycarboxylic acid organosilicon compound pMLSA, comprising the steps of:
step S1, weighing the reactant 4, 4-dibromobiphenyl (6.24g,20mmol), adding the reactant into a 250mL double-mouth bottle with a stirrer under the argon atmosphere, wherein one mouth of the double-mouth bottle is connected with a constant pressure dropping funnel. 150mL of anhydrous ether (i.e., the first solvent) was further added to the double-necked flask, stirring was performed to dissolve 4, 4-dibromobiphenyl, the temperature was cooled to 0 deg.C (i.e., the first temperature), and an n-hexane solution of n-butyllithium (1.6mol/L,12.5mL) was added dropwise, and the first lithiation reaction was performed for 1.5 hours while maintaining 0 deg.C (i.e., the second temperature). Slowly dropwise adding (TMS) 2 SiCl 2 (2.5mL,10.2mmol) was added to the reaction and the reaction was continued at 0 ℃ for 2h, then allowed to warm to room temperature naturally overnight. After the reaction is finished, dropwise adding saturated ammonium chloride aqueous solution to quench a reaction system, then removing an organic solvent by using a rotary evaporator, extracting the residual water phase for 3 times by using dichloromethane, collecting an organic phase, washing by using saturated NaCl aqueous solution, drying and filtering by using anhydrous magnesium sulfate, and obtaining a crude product pMLSA-Br after spin-drying the filtrate, wherein the compound is purified by column chromatography, and normal hexane is used as an eluent, so that a pure intermediate pMLSA-Br (4.6g,7.1mmol) can be obtained, the yield is 71.2%, and the structure is as follows;
step S2, weighing pMLSA-Br (6.6g,10.0mmol), adding into a 250mL double-mouth bottle under argon atmosphere, adding 120mL of anhydrous tetrahydrofuran (namely a second solvent), cooling to-78 ℃ (namely a third temperature), dropwise adding n-hexane solution of n-butyllithium (2.5mol/L,4.8mL), keeping the temperature, carrying out a second lithiation reaction, and reacting for 2 h. CO dried by concentrated sulfuric acid is introduced into the system at-78 DEG C 2 And (5) naturally heating the gas for 1h to room temperature, and continuously stirring and reacting for 5 h. After the reaction, the reaction system was quenched with 1M diluted hydrochloric acid solution and the pH of the system was adjusted to 3. Adding NaCl aqueous solution and extracting the aqueous phase 3 times with ethyl acetate, collecting the organic phase, washing the collected organic phase with saturated NaCl aqueous solution, drying over anhydrous magnesium sulfate and filtering, spin-drying the filtrate to obtain the crude product pMLSA, which is eluted by column chromatography, ethyl acetate: petroleum ether: acetic acid 12:50:1 as eluent, pure trisilyl polycarboxylic acid organosilicon compound pMLSA (4.0g,7.0mmol) was obtained in 70.1% yield, and the structural formula is shown in formula ii in fig. 1.
< example 3>
This example provides a method for synthesizing trisilyl polycarboxylic acid organosilicon compound STSA, comprising the steps of:
step S1, reactant 4,4 '-dibromo-2, 2' -diiodo-5, 5 '-dimethoxy-1, 1' -biphenyl (6.4g,10.0mmol) was weighed and added to a 250mL two-necked flask under argon atmosphere, one of which was connected to a constant pressure dropping funnel. 50mL of anhydrous tetrahydrofuran (i.e., a first solvent) was further added to the double-neck flask, and stirred to dissolve 4,4 '-dibromo-2, 2' -diiodo-5, 5 '-dimethoxy-1, 1' -biphenyl, the temperature was cooled to-90 ℃ (i.e., a first temperature), and a n-hexane solution of n-butyllithium (2.5mol/L,9.2mL) was added dropwise to conduct a first lithiation reaction for 2 hours while maintaining-90 ℃ (i.e., a second temperature). Slowly dropwise adding (TMS) 2 SiCl 2 (2.1mL,10.0mmol) is added into the reaction system, the temperature is kept at minus 90 ℃ for reaction for 2h, then the temperature is naturally raised to room temperature, and the reaction is continued overnight. After the reaction is finished, saturated ammonium chloride aqueous solution is dripped to quench the reaction system, and the solvent and other volatile matters are pumped to dryness by using a vacuum cold trap system. Saturated aqueous NaCl solution andextracting with dichloromethane for 3 times, collecting organic phase, drying with anhydrous magnesium sulfate, filtering, spin-drying the filtrate to obtain crude STSA-Br, purifying by column chromatography, and purifying with ethyl acetate: petroleum ether 1:5 as eluent gave pure intermediate STSA-Br (1.5g,2.8mmol) in 27.8% yield, of the following structure;
step S2, weighing STSA-Br (1.3g,2.4mmol), adding into a 250mL double-neck bottle under argon atmosphere, adding 50mL of anhydrous tetrahydrofuran (namely a second solvent), cooling to-78 ℃ (namely a third temperature), dropwise adding n-hexane solution of n-butyllithium (2.5mol/L,4.0mL), keeping the temperature, carrying out a second lithiation reaction, and reacting for 2 h. CO dried by concentrated sulfuric acid is introduced into the system at-78 DEG C 2 And (5) naturally heating the gas for 1h to room temperature, and continuously stirring and reacting for 5 h. After the reaction, the reaction system was quenched with 1M diluted hydrochloric acid solution and the pH of the system was adjusted to 3. Adding saturated NaCl aqueous solution and extracting the aqueous phase 3 times with ethyl acetate, collecting the organic phase, washing the collected organic phase with saturated NaCl aqueous solution, drying with anhydrous magnesium sulfate and filtering, spin-drying the filtrate to obtain crude product STSA, eluting the compound by column chromatography, and eluting with ethyl acetate: petroleum ether: pure trisilyl polycarboxylic acid organosilicon compound STSA (0.75g,1.5mmol) was obtained in 65.9% yield using acetic acid ═ 10:30:1 as the eluent, and the structural formula is shown in formula iii in fig. 1.
< example 4>
This example provides a method for synthesizing trisilyl polycarboxylic acid organosilicon compound STSDA, comprising the steps of:
step S1, the reactant 1,3,5 tribromobenzene (6.0g,18.9mmol) was weighed and added to a 250mL two-necked flask under argon atmosphere, one of the two-necked flask was connected to a constant pressure dropping funnel. Adding 170mL of anhydrous diethyl ether (i.e., first solvent) into the double-neck flask, stirring to dissolve 1,3,5 tribromobenzene, cooling to-78 deg.C (i.e., first temperature), adding dropwise n-hexane solution of n-butyllithium (1.6mol/L,13.2mL), and maintaining at-78 deg.C (i.e., second temperature)) The first lithiation reaction was carried out for 2 h. Slowly dropwise adding (TMS) 2 SiCl 2 (2.3mL,9.5mmol) is added into the reaction system, the temperature is kept at-78 ℃ for reaction for 2h, then the temperature is naturally raised to room temperature, and the reaction is continued overnight. After the reaction is finished, dropwise adding a saturated ammonium chloride aqueous solution to quench a reaction system, adding saturated saline solution and adding ethyl acetate to extract a water phase for 3 times, collecting an organic phase, washing with a saturated NaCl aqueous solution, drying and filtering with anhydrous magnesium sulfate, and spin-drying the filtrate to obtain a crude product TSDA-Br, wherein the compound is purified by column chromatography, and n-hexane is used as an eluent to obtain a pure intermediate TSDA-Br (2.4g,3.8mmol), the yield is 39.8%, and the structure is as follows;
step S2, weighing TSDA-Br (1.3g,2.0mmol), adding into a 100mL double-neck flask under argon atmosphere, adding 70mL of anhydrous tetrahydrofuran (namely a second solvent), cooling to-78 ℃ (namely a third temperature), dropwise adding n-hexane solution of n-butyllithium (2.4mol/L,2.0mL), keeping the temperature, carrying out a second lithiation reaction, and reacting for 2 h. CO dried by concentrated sulfuric acid is introduced into the system at-78 DEG C 2 And (5) naturally raising the temperature to room temperature after 1h of gas, heating to 60 ℃, and continuously stirring for reacting for 5 h. After the reaction, the reaction system was quenched with 1M diluted hydrochloric acid solution and the pH of the system was adjusted to 3. Adding saturated NaCl aqueous solution, extracting the aqueous phase for 3 times by using ethyl acetate, collecting an organic phase, washing the collected organic phase by using the saturated NaCl aqueous solution, drying by using anhydrous magnesium sulfate, filtering, and spin-drying the filtrate to obtain a crude product STSDA, wherein the compound is eluted by column chromatography, and n-hexane: ethyl acetate: acetic acid 30: 10: 1 as eluent, pure trisilylpolycarboxylic organosilicon compound STSDA (0.75g,1.3mmol) was obtained in 67.2% yield, and the structural formula is shown in formula IV in FIG. 1.
< example 5>
This example provides a method for synthesizing a trisilyl polycarboxylic acid organosilicon compound TSDA, comprising the following steps:
step S1 corresponds to step S1 of example 4;
step (ii) ofS2, weighing TSDA-Br (1.3g,2.0mmol), adding into a 100mL double-neck flask under argon atmosphere, adding 70mL of anhydrous tetrahydrofuran (namely a second solvent), cooling to-78 ℃ (namely a third temperature), dropwise adding a n-hexane solution of tert-butyl lithium (1.3mol/L,13.5mL), keeping the temperature for carrying out a second lithiation reaction, and reacting for 2 h. CO dried by concentrated sulfuric acid is introduced into the system at-78 DEG C 2 And (5) naturally raising the temperature to room temperature after 1h of gas, heating to 60 ℃, and continuously stirring for reacting for 5 h. After the reaction, the reaction system was quenched with 1M diluted hydrochloric acid solution and the pH of the system was adjusted to 3. Adding saturated NaCl aqueous solution, extracting the aqueous phase for 3 times by using ethyl acetate, collecting an organic phase, washing the collected organic phase by using the saturated NaCl aqueous solution, drying by using anhydrous magnesium sulfate, filtering, and spin-drying the filtrate to obtain a crude product TSDA, wherein the compound is eluted by column chromatography, and n-hexane: methanol: ethyl acetate: acetic acid 30:1:10:5 as eluent, pure trisilyl polycarboxylic acid organosilicon compound TSDA (0.75g,1.3mmol) can be obtained with a yield of 30.1%, and the structural formula is shown as formula V in figure 1.
< example 6>
This example provides a method for synthesizing a trisilyl polycarboxylic acid organosilicon compound TLDA, comprising the following steps:
step S1, reactant 3, 5-dibromo-4 '-iodo-1, 1' -biphenyl (4.4g,10.0mmol) was weighed and added to a 250mL two-necked flask under argon atmosphere, one of the two-necked flask was connected to a constant pressure dropping funnel. 170mL of anhydrous ether (i.e., the first solvent) was further added to the double-necked flask, and the mixture was stirred to prepare 3, 5-dibromo-4 '-iodo-1, 1' -biphenyl, and the temperature was cooled to-78 deg.C (i.e., the first temperature), and a n-hexane solution of n-butyllithium (1.6mol/L,6.4mL) was added dropwise, and the mixture was subjected to the first lithiation reaction for 2 hours while maintaining-78 deg.C (i.e., the second temperature). Slowly dropwise adding (TMS) 2 SiCl 2 (1.3mL,5.2mmol) is added into the reaction system, the temperature is kept at-78 ℃ for reaction for 2h, then the temperature is naturally raised to room temperature, and the reaction is continued overnight. After the reaction is finished, dropwise adding saturated ammonium chloride aqueous solution to quench a reaction system, adding saturated saline solution and adding ethyl acetate to extract a water phase for 3 times, collecting an organic phase, washing with saturated NaCl aqueous solution, drying and filtering with anhydrous magnesium sulfate, and spin-drying the filtrate to obtain a crude product TLDA-Br, wherein the compound is purified by column chromatographyUsing n-hexane as eluent to obtain pure intermediate TLDA-Br (1.6g,2.0mmol), yield 39.8%, structure as shown in the following formula;
step S2, weighing TLDA-Br (0.8g,1.0mmol), adding into a 100mL double-neck flask under argon atmosphere, adding 50mL of anhydrous tetrahydrofuran (i.e. a second solvent), cooling to-78 ℃ (i.e. a third temperature), dropwise adding a n-hexane solution of tert-butyl lithium (1.3mol/L,7.4mL), keeping the temperature for carrying out a second lithiation reaction, and reacting for 2 h. CO dried by concentrated sulfuric acid is introduced into the system at-78 DEG C 2 And (5) naturally raising the temperature to room temperature after 1h of gas, heating to 60 ℃, and continuously stirring for reacting for 5 h. After the reaction, the reaction system was quenched with 1M diluted hydrochloric acid solution and the pH of the system was adjusted to 3. Adding saturated NaCl aqueous solution, extracting the aqueous phase for 3 times by using ethyl acetate, collecting an organic phase, washing the collected organic phase by using the saturated NaCl aqueous solution, drying by using anhydrous magnesium sulfate, filtering, and spin-drying the filtrate to obtain a crude product TLDA, wherein the compound is eluted by column chromatography, and n-hexane: methanol: ethyl acetate: pure trisilyl polycarboxylic acid organosilicon compound TLDA (0.085g,0.13mmol) can be obtained by using acetic acid as eluent, wherein the acetic acid is 20:3:8:5, the yield is 13.2%, and the structural formula is shown as a formula VI in a figure 1.
The trisilyl polycarboxylic acid organosilicon compounds mMTSA, pMLSA, STSA, STSDA, TSDA and TLDA prepared in the above examples were reacted with a metal salt Zn (NO) 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·5H 2 O、Cd(NO 3 ) 2 ·4H 2 O and In (NO) 3 ) 2 ·6H 2 And O adopts a solvothermal method to prepare SiMOFs.
1. Zn (NO) was weighed separately 3 ) 2 ·6H 2 O (3.0mg,0.010mmol) and mMSTA (4.0mg,0.010mmol) were placed in a 10mL glass tube, 0.3mL DMF, 2.0mL EA and 0.2mL deionized water were added to the tube in this order, and the resulting mixture was ultrasonically dissolved and the tube was sealed. Standing the test tube on a 60 deg.C metal bath heater for heating for 72h to obtainThe colorless crystals photoresponse SiMOF-1. After activation based on the metal salt Zn (NO) used 3 ) 2 ·6H 2 The SiMOF-1 yield was calculated to be about 53.4% on a molar basis for O.
2. Zn (NO) was weighed separately 3 ) 2 ·6H 2 O (3.0mg,0.010mmol) and pMLSA (5.0mg,0.010mmol) were placed in a 10mL glass tube, and 1.0mL DMF, 2.0mL MeOH and 0.5mL deionized water were added to the tube in this order, and the resulting mixture was ultrasonically dissolved and the tube was sealed. And standing the test tube on a metal bath heater at the temperature of 80 ℃ and heating for 48h to obtain the colorless crystal photoresponse SiMOF-2. After activation based on the metal salt Zn (NO) used 3 ) 2 ·6H 2 The SiMOF-2 yield was approximately 43.1% calculated on the molar amount of O.
3. Zn (NO) was weighed separately 3 ) 2 ·6H 2 O (6.0mg,0.12mmol), 4' -bipyridine (1.8mg,0.10mmol) and TSDA (5.0mg,0.011mmol) were put in a 10mL glass tube, and 1.5mL of DMF and 1.0mL of deionized water were added to the tube in this order, and the resulting mixture was ultrasonically dissolved and the tube was sealed. Standing the test tube on a flat plate heater at 60 ℃ for 72h to obtain a colorless crystal SiMOF-3. After activation based on the metal salt Zn (NO) used 3 ) 2 ·6H 2 The SiMOF-3 yield was approximately 49.1% calculated on the molar amount of O.
4. Cd (NO) were weighed separately 3 ) 2 ·6H 2 O (5.0mg,0.018mmol) and TSDA (5.0mg,0.011mmol) were placed in a 10mL glass tube, 2.0mL DMF and 1.0mL deionized water were added to the tube in this order, and the resulting mixture was ultrasonically dissolved and the tube was sealed. Standing the test tube on a flat heater at 60 ℃ for 72h to obtain colorless crystals, namely SiMOF-4. After activation, based on the metal salt Cd (NO) used 3 ) 2 ·6H 2 The SiMOF-4 yield was approximately 58.3% calculated on the molar amount of O.
5. Separately weigh Cu (NO) 3 ) 2 ·6H 2 O (6.0mg,0.018mmol) and TSDA (5.0mg,0.011mmol) were placed in a 10mL glass tube, 2.0mL DMF and 0.5mL deionized water were added to the tube in this order, and the resulting mixture was ultrasonically dissolved and the tube was sealed. The test tube is placed stillAnd (3) heating the mixture for 72 hours at the temperature of 85 ℃ to obtain blue hexagonal crystals, namely SiMOF-5. Cu (NO) based on the metal salt used after activation 3 ) 2 ·6H 2 The SiMOF-5 yield was about 18.3% calculated on the molar amount of O.
6. In (NO) was weighed separately 3 ) 2 ·6H 2 O (6.0mg,0.20mmol) and TSDA (4.0mg,0.010mmol) were placed in a 10mL glass tube, 2.0mL DMF and 0.5mL deionized water and 0.2mL dilute nitric acid solution (1.0M) were added to the tube in that order, and the resulting mixture was ultrasonically dissolved and the tube was sealed. The test tube is stood on a flat heater at 85 ℃ for 72h to obtain colorless crystals, namely SiMOF-6. In (NO) after activation based on the metal salt used 3 ) 2 ·6H 2 The SiMOF-6 yield was calculated to be about 47.2% on a molar basis for O.
7. Zn (NO) was weighed separately 3 ) 2 ·6H 2 O (6.0mg,0.12mmol), 4,4' -bipyridine (1.8mg,0.10mmol) and TLDA (5.8mg,0.011mmol) were put in a 10mL glass tube, 3.0mL of DMF and 1.0mL of MeOH were added to the tube in this order, and the resulting mixture was ultrasonically dissolved and the tube was sealed. The tube was stood on a flat plate heater at 100 ℃ for 72 hours to give a colorless crystal SiMOF-7. After activation based on the metal salt Zn (NO) used 3 ) 2 ·6H 2 The SiMOF-7 yield was about 38.1% calculated on the molar amount of O.
8. Cd (NO) were weighed separately 3 ) 2 ·6H 2 O (5.0mg,0.018mmol) and TLDA (5.8mg,0.011mmol) were placed in a 10mL glass tube, 2.5mL DMF, 1.0mL MeOH, and 1.0mL deionized water were added to the tube in this order, and the resulting mixture was ultrasonically dissolved and the tube was sealed. Standing the test tube on a flat heater at 60 ℃ for 72h to obtain a colorless crystal, namely SiMOF-8. After activation, based on the metal salt Cd (NO) used 3 ) 2 ·6H 2 The calculated molar amount of O gives a SiMOF-8 yield of about 58.3%.
The trisilyl polycarboxylic organosilicon compounds mMTSA, STSA, STSD A and TSDA prepared in the above examples and their intermediates mMTSA-Br, STSA-Br and TSDA-Br were subjected to Fourier transform infrared spectroscopy, high resolution mass spectroscopy, nuclear magnetic resonance hydrogen spectroscopy, nuclear magnetic resonance carbon spectroscopy and nuclear magnetic resonance silicon spectroscopy test characterization, and the organosilicon compound STSD DA in example 4 and SiMOF-1, SiMOF-3, SiMOF-4, SiMOF-5 and SiMOF-6 prepared based on the trisilyl polycarboxylic organosilicon compounds were subjected to single crystal X-ray diffraction test characterization, and powder X-ray diffraction test, thermogravimetric analysis and fluorescence test were performed on SiMOF-1. The results are shown below:
mMTSA-Br：
1 H NMR(600MHz,CDCl 3 )δ7.53(s,2H),7.47(d,J＝8.0Hz,2H),7.34(d,J＝7.3Hz,2H),7.21(t,J＝7.6Hz,2H),0.19(s,18H)；
13 C NMR(151MHz,CDCl 3 )δ139.0,138.2,134.3,131.6,129.9,123.2,-0.5；
29 Si NMR(119MHz,DMSO)δ-15.5,-37.7；
IR(cm -1 ):2952(w),1686(s),1552(m),1430(s),1280(s),1146(m),930(w),833(s),769(w),697(s),674(s),622(w),560(w),520(w)；
HRMS(ESI):m/z[M+Na] + calcd for C 28 H 22 O 6 Si:508.9582,found:508.9585。
mMTSA：
1 H NMR(600MHz,DMSO)δ12.98(s,2H),8.03(s,2H),7.93(d,J＝7.8Hz,2H),7.61(d,J＝7.3Hz,2H),7.53(t,J＝7.6Hz,2H),0.17(s,18H)；
13 C NMR(151MHz,CD 3 OD)δ170.0,141.5,138.3,137.5,131.6,131.1,129.4,-0.3；
29 Si NMR(119MHz,DMSO)δ-15.8,-38.5；
IR(cm -1 ):2950(w),1742(w),1678(s),1573(m),1476(w),1420(m),1398(m),1290(s),1243(s),1170(w),1138(w),1099(w),944(m),827(s),748(m),684(s),654(m),552(w),507(m)；
HRMS(ESI):m/z[M+Na] + calcd for C 28 H 22 O 6 Si:434.1643,found:434.1670。
STSA-Br：
1 H NMR(400MHz,CDCl 3 )δ7.68(s,2H),7.36(s,2H),4.03(s,6H),0.11(s,18H)；
13 C NMR(101MHz,CDCl 3 )δ156.59,148.49,137.09,133.08,111.75,105.27,56.26,-1.07；
29 Si NMR(119MHz,DMSO)δ-14.09,-40.32；
IR(cm -1 ):2942(w),1579(m),1529(w),1438(m),1432(m),1234(s),1045(s),830(s),691(s),610(m)；
HRMS(ESI):m/z[M] + calcd for C 20 H 28 Br 2 O 2 Si 3 :541.9764,found:541.9761。
STSA：
1 H NMR(400MHz,DMSO)δ12.78(s,2H),7.78(s,2H),7.39(s,2H),4.00(s,6H),0.02(s,18H)；
13 C NMR(101MHz,DMSO)δ167.64,161.72,150.31,134.65,126.46,121.65,106.68,56.81,2.25；
IR(cm -1 ):2964(w),1682(m),1593(m),1408(w),1389(w),1257(m),1241(m),1212(m),1084(m),1047(s),1014(s),792(s),742(w),688(m),672(m)；HRMS(ESI):m/z[M+Na] + calcd for C 22 H 30 O 6 NaSi 3 :497.1248,found:497.1212。
TSDA-Br:
1 H NMR(600MHz,CDCl 3 )δ7.66(s,2H,Ar-CH),7.40(s,4H,Ar-CH),0.21(s,18H,Si(CH 3 ) 3 )；
13 C NMR(151MHz,CDCl 3 )δ140.9,136.5,134.4,123.6,-0.5；
29 Si NMR(119MHz,CDCl 3 )δ-15.3,-36.2；
IR(cm -1 ):2951(w),1556(m),1534(s),1416(w),1377(m),1354(m),1245(s),1113(s),1099(s),853(s)，831(s),734(s),692(m),672(s),626(m),523(m)；
m/z[M+Na] + calcd for C 18 H 24 Br 4 NaSi 3 :662.7817,found:662.7819。
STSDA:
1 H NMR(600MHz,DMSO)δ12.98(s,2H),7.95(s,2H),7.86(s,2H),7.51(s,2H),0.07(s,18H)；
13 C NMR(151MHz,DMSO)δ165.9,141.1,138.7,134.6,133.0,132.2,122.5,-1.0.IR(cm -1 ):2951(w),2647(w),2525(w),1536(m),1552(m),1420(m),1381(m),1354(w),1282(m),1245(m),1146(w),1115(w),1111(w),930(w),834(s),769(w),734(w),695(m),674(m),625(w),565(w),521(m)；
HRMS(ESI):m/z[M] + calcd for C 20 H 26 O 4 Si 3 Br 2 :574.4825,found:574.4870。
TSDA:
1 H NMR(600MHz,Methanol-d 4 )δ8.64(s,2H,Ar-CH),8.35(s,4H,Ar-CH),0.26(s,18H,Si(CH 3 ) 3 )；
13 C NMR(151MHz,Methanol-d 4 )δ169.0,142.0,138.1,132.4,-0.4； 29 Si NMR(119MHz,CDCl 3 )δ-15.3,-37.7.
IR(cm -1 ):2951(w),2647(w),2525(w),1589(w),1690(s),1428(w),1253(s),1167(w),1128(w),827(s),750(m),690(s),676(m),633(w),585(w),524(w)；
HRMS(ESI):m/z[M+Na] + calcd for C 22 H 28 O 8 NaSi 3 :527.0990,found:527.0984。
FIG. 2 is a nuclear magnetic hydrogen spectrum of intermediate mMTSA-Br in example 1 of the present invention; FIG. 3 is a nuclear magnetic carbon spectrum of intermediate mMTSA-Br in example 1 of the present invention; FIG. 4 is a nuclear magnetic silicon spectrum of intermediate mMTSA-Br in example 1 of the present invention. The nuclear magnetic results, shown in FIGS. 2, 3 and 4, indicate that the synthesized compound is the theoretical intermediate mMTSA-Br of example 1.
FIG. 5 is a nuclear magnetic hydrogen spectrum of organosilicon compound mMTSA in example 1 of the present invention; FIG. 6 is a nuclear magnetic carbon spectrum of organosilicon compound mMTSA in example 1 of the present invention; FIG. 7 shows nuclear magnetic silicon spectra of organosilicon compound mMTSA in example 1 of the present invention. As shown in fig. 5, 6 and 7, the nuclear magnetic results indicate that the synthesized compound is the theoretical organosilicon compound mtsa of example 1.
FIG. 8 is a nuclear magnetic hydrogen spectrum of an intermediate STSA-Br in example 3 of the present invention; FIG. 9 is a nuclear magnetic carbon spectrum of the intermediate STSA-Br of example 3 of the present invention; FIG. 10 shows the nuclear magnetic silicon spectrum of the intermediate STSA-Br in example 3 of the present invention. The nuclear magnetic results, shown in FIGS. 8, 9 and 10, indicate that the synthesized compound is the theoretical intermediate STSA-Br of example 3.
FIG. 11 is a nuclear magnetic hydrogen spectrum of intermediate TSDA-Br in example 4 of the present invention; FIG. 12 is a nuclear magnetic carbon spectrum of intermediate TSDA-Br in example 4 of the present invention; FIG. 13 is a nuclear magnetic silica spectrum of intermediate TSDA-Br in example 4 of the present invention. The nuclear magnetic results, shown in FIGS. 11, 12 and 13, indicate that the synthesized compound is TSDA-Br, the theoretical intermediate of example 4.
FIG. 14 is a nuclear magnetic hydrogen spectrum of organosilicon compound STSDA in example 4 of the present invention; FIG. 15 shows the nuclear magnetic carbon spectrum of organosilicon compound STSDA in example 4 of the present invention. As shown in fig. 14 and 15, the nuclear magnetic results indicate that the synthesized compound is the theoretical organosilicon compound STSDA of example 4.
FIG. 16 is a nuclear magnetic hydrogen spectrum of an organosilicon compound TSDA in example 5 of the present invention; FIG. 17 is a nuclear magnetic carbon spectrum of an organosilicon compound TSDA in example 5 of the present invention; FIG. 18 is a nuclear magnetic silicon spectrum of an organosilicon compound TSDA in example 5 of the present invention. As shown in fig. 16, 17 and 18, the nuclear magnetic results indicate that the synthesized compound is the theoretical organosilicon compound TSDA of example 5.
FIG. 19 is a schematic diagram showing the crystal structure and stacking of the organosilicon compound STSDA in example 4 of the present invention. As shown in fig. 19, it was confirmed again that STSDA, a target product, was obtained by the crystal structure. In addition, the adjacent-COOH between 2 STSDA molecules forms strong hydrogen bonds (i.e. C-OH … O) and self-assembles to form a hydrogen bond-containing three-dimensional organic structure (HOF), which indicates that the formed organosilicon compound has a novel structure.
FIG. 20 is a schematic representation of the crystal structure of SiMOF-1 made from an example based trisilyl polycarboxylic acid organosilicon compound of the present invention. FIG. 21 is a schematic representation of the crystal structure of SiMOF-3 made from an example-based trisilylpolycarboxylic acid organosilicon compound of the present invention. FIG. 22 is a schematic representation of the crystal structure of SiMOF-4 made from an example based trisilyl polycarboxylic acid organosilicon compound of the present invention. As can be seen from FIG. 20, in SiMOF-1, each of the units is averagedZn 2+ In addition to coordination to the 3O atoms of-COOH on mMSTA, coordination to 1 DMF molecule forms a tetra-coordinated Zn 2+ A metal cluster center; as can be seen from FIG. 21, in SiMOF-3, on average every 2 Zn are linked to 4-COOH groups on the TSDA to form an octagonal Zn metal cluster center, 3O groups of Zn1 and 3-COOH and 1H group 2 The O molecule coordinates to form a 4-coordinate, whereas Zn2 is attached in a slightly different manner, not only sharing 3O atoms of-COOH with Zn1, but also forming a 5-coordinate with 2O atoms already having another 1-COOH; as can be seen from FIG. 22, in SiMOF-4, every 2 Cd are connected with 4-COOH to form a six-coordinated Cd metal cluster center, and Cd are 6-coordinated with 4O of 2-COOH and O atoms of 2-COOH.
FIG. 23 is a schematic representation of the topology of SiMOF-5 made based on the example trisilyl polycarboxylic acid organosilicon compounds. FIG. 24 is a schematic of the topology of SiMOF-6 made based on the example trisilyl polycarboxylic acid organosilicon compounds. As shown in FIGS. 23 and 24, the ssa topology type of (4,4-c) network structure is formed in SiMOF-5 and the can topology type of (4-c) network structure is formed in SiMOF-6.
FIG. 25 is a powder X-ray diffraction contrast plot of SiMOF-1 prepared based on the trisilylpolycarboxylic acid organosilicon compounds of the examples. As shown in FIG. 25, the PXRD curves of the synthesized and activated SiMOF-1 are very similar to those simulated from the single crystal, which indicates that the synthesized SiMOF-1 has high purity and no impurity doping, and the framework structure of the SiMOF-1 has good air stability.
FIG. 26 is a thermogravimetric plot of SiMOF-1 prepared based on the trisilylpolycarboxylic acid organosilicon compounds of the examples. As shown in fig. 26, it can be seen that there is a weight loss of 13.2% before 385 ℃, which is consistent with the mass ratio of DMF molecules calculated according to the formula, indicating that this mass loss belongs to 2 DMF molecules, which also indicates that DMF molecules do not exchange with EtOH during the solvent exchange process due to participation in coordination during the activation process. SiMOF-1 does not start to decompose until 385 ℃, which is indicative of the high thermal stability of the organo-silicon metal-organic framework.
FIG. 27 is a graph of the fluorescence of SiMOF-1 prepared based on the trisilylpolycarboxylic acid organosilicon compounds of the examples. As shown in FIG. 27, the maximum emission wavelengths of SiMOF-1 under excitation at 275nm, 300nm and 320nm were 412nm, 407nm and 381nm, respectively. In the range of 275-320 nm, emitted light can generate blue shift when SiMOF-1 is excited by light with longer wavelength.
The foregoing is a detailed description of embodiments that will enable those skilled in the art to make and use the invention. The technical solutions of the present invention, which can be improved or modified only by analysis, analogy or limited enumeration, should be within the scope of protection determined by the claims.
Claims (10)
1. A trisilyl polycarboxylic acid organosilicon compound, characterized in that the trisilyl polycarboxylic acid organosilicon compound is any one of organosilicon compound mMTSA, organosilicon compound pMLSA, organosilicon compound STSA, organosilicon compound STSDA, organosilicon compound TSDA and organosilicon compound TLDA,
wherein the structural formulas of the organosilicon compound mMTSA, the organosilicon compound pMLSA, the organosilicon compound STSA, the organosilicon compound STSDA, the organosilicon compound TSDA and the organosilicon compound TLDA are respectively shown as the following formulas I-VI:
2. a method of synthesizing the trisilyl polycarboxylic acid organosilicon compound of claim 1, comprising the steps of:
step S1, adding n-hexane solution of n-butyllithium into the first solvent solution of the reactant at a first temperature without water and oxygen, carrying out a first lithiation reaction at a second temperature in the reaction system, and dropwise adding (TMS) at the first temperature after the first lithiation reaction is finished 2 SiCl 2 And (4) continuing the reaction, naturally heating to room temperature after the reaction is finished, and continuing the reaction overnight. Saturated ammonium chloride for reaction completionQuenching the reaction system with water solution, removing organic solvent, extracting, washing, drying, concentrating and purifying to obtain intermediate;
step S2, adding a normal hexane solution of a lithium reagent into the second solvent solution of the intermediate at a third anhydrous and oxygen-free temperature, carrying out a second lithiation reaction of the reaction system at the third temperature, and introducing dry CO at the third reaction temperature after the second lithiation reaction is finished 2 And (4) reacting, naturally heating to room temperature or heating to continue stirring for reaction after the reaction is finished. And after the reaction is finished, quenching the reaction system by using a dilute hydrochloric acid solution, adjusting the pH value to acidity, extracting, washing, drying, concentrating and purifying to obtain the trisilyl polycarboxylic acid organic silicon compound.
3. The method for synthesizing trisilyl polycarboxylic acid organosilicon compound according to claim 2, wherein said trisilyl polycarboxylic acid organosilicon compound is said organosilicon compound mMTSA,
in the step S1, the first temperature is-78 ℃, the reactant is m-dibromobenzene, the first solvent is tetrahydrofuran, the second temperature is-48 ℃, the time of the first lithiation reaction is 1h, and the intermediate is mMTSA-Br;
in the step S2, the third temperature is-78 ℃, the second solvent is tetrahydrofuran, the lithium reagent is n-butyllithium, and the time of the second lithiation reaction is 2 hours.
4. The method of synthesizing trisilyl polycarboxylic acid organosilicon compound according to claim 2, wherein said trisilyl polycarboxylic acid organosilicon compound is said organosilicon compound pMLSA,
in the step S1, the first temperature is 0 ℃, the reactant is 4, 4-dibromobiphenyl, the first solvent is diethyl ether, the second temperature is 0 ℃, the time of the first lithiation reaction is 1.5h, and the intermediate is pMLSA-Br;
in the step S2, the third temperature is-78 ℃, the second solvent is tetrahydrofuran, the lithium reagent is n-butyllithium, and the time of the second lithiation reaction is 2 hours.
5. The method according to claim 2, wherein the trisilyl polycarboxylic acid organosilicon compound is the organosilicon compound STSA,
in the step S1, the first temperature is-90 ℃, the reactant is 4,4 '-dibromo-2, 2' -diiodo-5, 5 '-dimethoxy-1, 1' -biphenyl, the first solvent is tetrahydrofuran, the second temperature is-90 ℃, the time of the first lithiation reaction is 2 hours, and the intermediate is STSA-Br;
in the step S2, the third temperature is-78 ℃, the second solvent is tetrahydrofuran, the lithium reagent is n-butyllithium, and the time of the second lithiation reaction is 2 hours.
6. The method according to claim 2, wherein the trisilyl polycarboxylic acid organosilicon compound is STSDA,
in the step S1, the first temperature is-78 ℃, the reactant is 1,3,5 tribromobenzene, the first solvent is diethyl ether, the second temperature is-78 ℃, the time of the first lithiation reaction is 2 hours, and the intermediate is TSDA-Br;
in the step S2, the third temperature is-78 ℃, the second solvent is tetrahydrofuran, the lithium reagent is n-butyllithium, and the time of the second lithiation reaction is 2 hours.
7. The method for synthesizing trisilyl polycarboxylic acid organosilicon compound according to claim 2, wherein said trisilyl polycarboxylic acid organosilicon compound is said organosilicon compound TSDA,
in the step S1, the first temperature is-78 ℃, the reactant is 1,3,5 tribromobenzene, the first solvent is diethyl ether, the second temperature is-78 ℃, the time of the first lithiation reaction is 2h, and the intermediate is TSDA-Br;
in the step S2, the third temperature is-78 ℃, the second solvent is tetrahydrofuran, the lithium reagent is tert-butyl lithium, and the time of the second lithiation reaction is 2 hours.
8. The method for synthesizing trisilyl polycarboxylic acid organosilicon compound according to claim 2, wherein said trisilyl polycarboxylic acid organosilicon compound is said organosilicon compound TLDA,
in the step S1, the first temperature is-78 ℃, the reactant is 3, 5-dibromo-4 '-iodo-1, 1' -biphenyl, the first solvent is diethyl ether, the second temperature is-78 ℃, the time of the first lithiation reaction is 2 hours, and the intermediate is TLDA-Br;
in the step S2, the third temperature is-78 ℃, the second solvent is tetrahydrofuran, the lithium reagent is tert-butyl lithium, and the time of the second lithiation reaction is 2 hours.
9. Use of the trisilyl polycarboxylic organosilicon compounds of claim 1 in the preparation of SiMOFs by solvothermal reaction with metal salts.
10. Use of trisilyl polycarboxylic organosilicon compounds according to claim 9 in the preparation of SiMOFs,
wherein the metal salt is Zn (NO) 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·5H 2 O、Cd(NO 3 ) 2 ·4H 2 O and In (NO) 3 ) 2 ·6H 2 O，
The temperature of the solvothermal is 60-100 ℃, and the time is 20-72 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210597054.5A CN114957310A (en) | 2022-05-30 | 2022-05-30 | Trisilyl polycarboxylic organic silicon compound and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210597054.5A CN114957310A (en) | 2022-05-30 | 2022-05-30 | Trisilyl polycarboxylic organic silicon compound and synthesis method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114957310A true CN114957310A (en) | 2022-08-30 |
Family
ID=82958555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210597054.5A Pending CN114957310A (en) | 2022-05-30 | 2022-05-30 | Trisilyl polycarboxylic organic silicon compound and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114957310A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117924705A (en) * | 2024-03-21 | 2024-04-26 | 华能(广东)能源开发有限公司海门电厂 | Organic silicon porous material Si-COF-EA based on biomass derivation and preparation and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734718A (en) * | 2018-11-29 | 2019-05-10 | 同济大学 | A kind of polycarboxylic acid organic ligand and synthetic method based on NDHPI modification |
| WO2019186134A1 (en) * | 2018-03-29 | 2019-10-03 | G2O Water Technologies Limited | Membranes comprising a layer of metal organic framework particles |
-
2022
- 2022-05-30 CN CN202210597054.5A patent/CN114957310A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019186134A1 (en) * | 2018-03-29 | 2019-10-03 | G2O Water Technologies Limited | Membranes comprising a layer of metal organic framework particles |
| CN109734718A (en) * | 2018-11-29 | 2019-05-10 | 同济大学 | A kind of polycarboxylic acid organic ligand and synthetic method based on NDHPI modification |
Non-Patent Citations (1)
| Title |
|---|
| BAOLING YUAN等，: "Delicate and Fast Photochemical Surface Modification of 2D Photoresponsive Organosilicon Metal–Organic Frameworks", 《ANGEW. CHEM. INT. ED.》, 19 May 2022 (2022-05-19), pages 1 - 6 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117924705A (en) * | 2024-03-21 | 2024-04-26 | 华能(广东)能源开发有限公司海门电厂 | Organic silicon porous material Si-COF-EA based on biomass derivation and preparation and application thereof |
| CN117924705B (en) * | 2024-03-21 | 2024-05-28 | 华能(广东)能源开发有限公司海门电厂 | Organic silicon porous material Si-COF-EA based on biomass derivation and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110218220B (en) | Functionalized metal-organic framework compound, complex formed by functionalized metal-organic framework compound, and preparation method and application of functionalized metal-organic framework compound | |
| Zhu et al. | Hydrothermal synthesis, crystal structures, and luminescent properties of a series of new lanthanide oxalatophosphonates with a layer architecture | |
| CN114957310A (en) | Trisilyl polycarboxylic organic silicon compound and synthesis method and application thereof | |
| Tian et al. | A microporous Cd-MOF based on a hexavalent silicon-centred connector and luminescence sensing of small molecules | |
| CN110684202A (en) | Two-dimensional layered imidazole copper C60Material, preparation method and application thereof | |
| CN109575062B (en) | Dinaphthyl carborane compound and preparation method and application thereof | |
| CN112029107B (en) | Triazine ligand-based two-dimensional metal organic framework material and preparation method and application thereof | |
| CN115819281B (en) | Cyano-substituted p-phenylene ethylene derivative, preparation method and application | |
| Ren et al. | Synthesis, crystal structure and thermal decomposition mechanism of complex [Sm (o-MBA) 3phen] 2 | |
| JP4420660B2 (en) | Organic borazine compound and process for producing the same | |
| CN110452388A (en) | A kind of preparation method of the hybridization porous polymer based on cage modle and trapezoidal-structure silsesquioxane | |
| JP7079494B2 (en) | New compound and its synthesis method | |
| CN110950861A (en) | Mononuclear dysprosium complex with 1, 10-phenanthroline-2, 9-dicarboxylic acid as ligand and preparation method and application thereof | |
| CN114874145A (en) | Water-soluble trityl free-based material and preparation method and application thereof | |
| CN113292607B (en) | Ionic luminescent platinum complex based on benzimidazole phosphine ligand and preparation method thereof | |
| CN114773614A (en) | Bimetal controllable distribution supramolecular material and preparation method thereof | |
| CN110330527B (en) | Mononuclear copper complex with fluorescence property and preparation method thereof | |
| CN110105160B (en) | Preparation method based on triphenylene alkyne type precursor and polycyclic aromatic hydrocarbon derivative thereof | |
| WO2023167278A1 (en) | Light-emitting material, oxygen sensor, and coating material | |
| CN114656646B (en) | Synthetic method of diarylene COFs material and application of diarylene COFs material in light-operated adsorption | |
| Liu et al. | Rare-earth (Eu3+, Tb3+) hybrids through amide bridge: Chemically bonded self-assembly and photophysical properties | |
| CN113816974B (en) | Porphyrin covalent connection sym-triazacyclonium compound and preparation and application thereof | |
| CN108822303B (en) | A kind of organic boron complexes and preparation method thereof with fluorescence property | |
| CN117069764A (en) | Bipyridine biphosphine copper complex, preparation method and application thereof | |
| CN114773222A (en) | Synthetic method of azo micromolecules for zinc oxide nanoparticle stable ligand |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |