CN111233822B - Crown ether modified ligand, four-metal Pt rectangular supramolecular complex, and preparation method and application thereof - Google Patents
Crown ether modified ligand, four-metal Pt rectangular supramolecular complex, and preparation method and application thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 63
- 239000002184 metal Substances 0.000 title claims abstract description 60
- 239000003446 ligand Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 150000003983 crown ethers Chemical class 0.000 title claims abstract description 29
- 238000010668 complexation reaction Methods 0.000 title description 2
- 239000000126 substance Substances 0.000 claims abstract description 11
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 229940125898 compound 5 Drugs 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- FGDJUEZBMFELRW-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl 4-methylbenzenesulfonate Chemical compound CC1=CC=C(S(=O)(=O)OCCOCCOCCOCCO)C=C1 FGDJUEZBMFELRW-UHFFFAOYSA-N 0.000 claims description 7
- 238000001917 fluorescence detection Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 5
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 5
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 claims description 4
- 229940075931 sodium dithionate Drugs 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 229940125782 compound 2 Drugs 0.000 claims description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 150000002678 macrocyclic compounds Chemical class 0.000 description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000013110 organic ligand Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- -1 alkenyl boric acid Chemical compound 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- GNXLDEFJAZGNCJ-UHFFFAOYSA-N tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate Chemical compound C1=CC(C(=O)OC(C)(C)C)=CC=C1B1OC(C)(C)C(C)(C)O1 GNXLDEFJAZGNCJ-UHFFFAOYSA-N 0.000 description 2
- LTZIIBSPYWTOQV-UHFFFAOYSA-N 2,7-dibromophenanthrene-9,10-dione Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3C(=O)C(=O)C2=C1 LTZIIBSPYWTOQV-UHFFFAOYSA-N 0.000 description 1
- KSNKQSPJFRQSEI-UHFFFAOYSA-N 3,3,3-trifluoropropanoic acid Chemical compound OC(=O)CC(F)(F)F KSNKQSPJFRQSEI-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- NZRBIKOOKFGDML-UHFFFAOYSA-N 4-bromo-1-[4-bromo-2-(bromomethyl)phenyl]-2-(bromomethyl)benzene Chemical group BrCC1=CC(Br)=CC=C1C1=CC=C(Br)C=C1CBr NZRBIKOOKFGDML-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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Abstract
The invention discloses a crown ether modified ligand, a four-metal Pt rectangular supramolecular complex, a preparation method and application thereof, wherein the four-metal Pt rectangular supramolecular complex has a chemical structural formula shown as Pt1 or Pt2,
tests show that the luminescent signal of the rectangular supermolecule complex of the four-metal Pt has strong response to ions of alkali metal ions and alkaline earth ions, and particularly Pt-1 can identify metal Na+Ion, Pt-2 rectangular supermolecule capable of recognizing metal Mg2+Ions.
Description
Technical Field
The invention belongs to the technical field of supramolecular synthesis and fluorescence detection, and relates to a crown ether modified ligand, a four-metal Pt rectangular supramolecular complex, a preparation method and application.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The supermolecule metal macrocyclic compound synthesized by a coordination-driven self-assembly method has received considerable attention of chemists of various countries in the world, and has potential application prospects in the aspects of selective recognition, sensing, reaction catalysis and the like due to the aesthetic appeal of the supermolecule metal macrocyclic compound on the structure and the chemical properties of a subject and an object. The rectangular molecule is one of many interesting metal supramolecular compounds, which is composed of many linear bidentate bridging ligands and various metal complexes with specific coordination geometry, such as a dinuclear Pt molecular clip, a dinuclear aromatic Ru complex and M (CO)3And (M ═ Mn, Re) core-complexes, etc., formed by coordinate bonding. However, through the research of the inventors of the present invention, the research on the rectangular metal supramolecular compound with sensing capability on the cation has not been reported at present.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a crown ether modified ligand, a four-metal Pt rectangular supramolecular complex, a preparation method and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in a first aspect, a crown ether modified ligand has the chemical structure formula L1Or L2As shown in the drawings, the above-described,
in a second aspect, a preparation method of crown ether modified ligand comprises the following reaction formula of taking a compound 1, tetraethyleneglycol p-toluenesulfonate and a compound 3 as raw materials to obtain L1A process for preparing the ligand compound;
or, the method comprises the following reaction formula of taking a compound 6, tetraethyleneglycol and a compound 3 as raw materials to obtain L2A process for preparing the ligand compound;
in the third aspect, the chemical structural formula of the four-metal Pt rectangular supramolecular complex is shown as Pt1 or Pt2,
in a fourth aspect, the preparation method of the rectangular supermolecule complex of the four metals Pt is obtained by reacting the ligand modified by the crown ether with a compound 5 under an alkaline condition, wherein the molar ratio of the ligand modified by the crown ether to the compound 5 is 1: 0.9-1.1;
the structural formula of compound 5 is:
et is ethyl.
The method adopts a one-pot method to obtain the four-metal Pt macrocyclic supermolecule, is simple to operate, and is easy to separate and purify. Meanwhile, the purity of the four-metal Pt macrocyclic supermolecule obtained by the preparation method is as high as 99.999%.
In a fifth aspect, the four-metal Pt rectangular supramolecular complex is applied to recognition and/or detection of alkali metal ions and/or alkaline earth metal ions.
In a sixth aspect, a method for identifying and/or detecting sodium ions, the four-metal Pt rectangular supramolecular complex is added into a solution to be detected for fluorescence detection;
wherein the four-metal Pt rectangular supramolecular complex is a compound shown by Pt1,
or, in the preparation method of the four-metal Pt rectangular supermolecule complex, the ligand modified by crown ether is L1The compounds shown.
In a seventh aspect, a method for identifying and/or detecting magnesium ions, the four-metal Pt rectangular supramolecular complex is added to a solution to be detected for fluorescence detection;
wherein the four-metal Pt rectangular supramolecular complex is a compound shown by Pt2,
or, in the preparation method of the four-metal Pt rectangular supermolecule complex, the ligand modified by crown ether is L2The compounds shown.
The invention has the beneficial effects that:
according to the invention, crown ether is firstly adopted to modify the ligand, then the crown ether modified ligand is adopted to prepare the four-metal Pt rectangular supramolecular complex, tests show that the luminescent signal of the four-metal Pt rectangular supramolecular complex has strong response to alkali metal ions and alkaline earth ions, and particularly Pt1 can identify metal Na+Ion, Pt2 rectangular supermolecule capable of recognizing metal Mg2+Ions.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows ligand L1 containing crown ether building blocks prepared in example 1 of the present invention1H NMR；
FIG. 2 shows ligand L2 containing crown ether building blocks prepared in example 2 of the present invention1H NMR；
FIG. 3 is a diagram of the preparation of metallic Pt rectangular supramolecular macrocycles Pt1 according to example 1 of the invention1H NMR；
Fig. 4 is a single crystal structure diagram of metallic Pt rectangular supramolecular macrocycle Pt1 prepared in example 1 of the present invention;
FIG. 5 is a diagram of the preparation of metallic Pt rectangular supramolecular macrocycles Pt2 according to example 2 of the invention1H NMR；
FIG. 6 is a diagram of the preparation of metallic Pt rectangular supramolecular macrocycles Pt2 according to example 2 of the invention31P NMR；
FIG. 7 is a diagram of the preparation of metallic Pt rectangular supramolecular macrocycles Pt2 according to example 2 of the invention13C NMR；
FIG. 8 is a graph showing the change of the emission spectrum of the titrated fluorescence in example 3 of the present invention: acetonitrile solution of Pt1 (concentration 1.5X 10)- 5M) titration solution (10 mM alkali metal or alkaline earth metal acetonitrile solution);
FIG. 9 is a graph showing the change of the emission spectrum of the titrated fluorescence of example 3 of the present invention: acetonitrile solution of Pt2 (concentration 1.5X 10)-5M) titration solution (10 mM alkali metal or alkaline earth metal acetonitrile solution).
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the fact that the existing rectangular metal supramolecular compound has no cation sensing capacity, the invention provides a crown ether modified ligand, a four-metal Pt rectangular supramolecular complex, a preparation method and application.
In a typical embodiment of the present invention, a crown ether modified ligand is provided, having a chemical structure formula as L1Or L2As shown in the drawings, the above-described,
in another embodiment of the invention, a preparation method of crown ether modified ligand is provided, which comprises the following reaction formula of obtaining L by using a compound 1, tetraethyleneglycol p-toluenesulfonate and a compound 3 as raw materials1A process for preparing the ligand compound;
or, the method comprises the following reaction formula of taking a compound 6, tetraethyleneglycol and a compound 3 as raw materials to obtain L2A process for preparing the ligand compound;
in one or more embodiments of this embodiment, the process for preparing compound 2 is: reacting the compound 1 with tetrabutylammonium bromide and sodium dithionate, and then adding tetraethylene glycol p-toluenesulfonate to react under an alkaline condition.
In one or more embodiments of this embodiment, the reaction to prepare compound 4 is a suzuki reaction. The Suzuki reaction is also called Suzuki coupling reaction and Suzuki-Miyaura reaction (Suzuki-Miyaura reaction), and is an organic coupling reaction, wherein aryl or alkenyl boric acid or boric acid ester and chlorine, bromine, iodo arene or olefin are subjected to cross coupling under the catalysis of a zero-valent palladium complex.
From compounds 4 to L1The reaction process of the ligand compound is a process of preparing a carboxyl group by hydrolysis in general.
In one or more embodiments of this embodiment, the reaction to prepare compound 7 is a substitution reaction.
In one or more embodiments of this embodiment, the reaction to prepare compound 8 is a suzuki reaction.
From compounds 8 to L2The reaction process of the ligand compound is a process of preparing a carboxyl group by hydrolysis in general.
The third embodiment of the invention provides a four-metal Pt rectangular supramolecular complex, the chemical structural formula of which is shown as Pt1 or Pt2,
in one or more examples of this embodiment, the single crystal formula of Pt1 is C225H300Cl6O27.50P12Pt6Has a chemical formula of [ Pt ]6(C36H30O9)3(PEt3)12(C14H8)3]·3(CH2Cl2)·0.5H2O。
In this series of examples, the single crystal of Pt1 crystallized in the triclinic system and belonged to the P-1 space group. One unit cell unit contains 1.5 metal Pt rectangular supermolecules, and six divalent Pt metal centers with different coordination environments; each divalent Pt metal center is bonded to a C atom, a carboxyl O atom and two P atoms on an anthracene, and is located in [ PtCP ]2O]Plane squareAnd (4) coordination environment.
The invention provides a preparation method of a four-metal Pt rectangular supramolecular complex, which is obtained by reacting the crown ether modified ligand with a compound 5 under an alkaline condition, wherein the molar ratio of the crown ether modified ligand to the compound 5 is 1: 0.9-1.1;
the structural formula of compound 5 is:
et is ethyl.
The method adopts a one-pot method to obtain the four-metal Pt macrocyclic supermolecule, is simple to operate, and is easy to separate and purify. Meanwhile, the purity of the four-metal Pt macrocyclic supermolecule obtained by the preparation method is as high as 99.999%.
The preparation reaction formula of Pt1 is as follows:
reaction conditions are as follows: (a) sodium dithionate, tetrabutylammonium bromide, tetrahydrofuran/water, room temperature; (b) refluxing tetra ethylene glycol p-toluenesulfonate and sodium hydroxide aqueous solution; (c) tetrakis (triphenylphosphine) palladium (5 mol%), potassium carbonate, dioxane/water, 100 ℃; (d) tetrafluoroboric acid-diethyl ether, dichloromethane; (e) sodium hydroxide, acetone/water, room temperature.
The preparation reaction formula of Pt2 is as follows:
reaction conditions are as follows: (f) tetraethylene glycol, sodium hydride and tetrahydrofuran at room temperature; (g) tetrakis (triphenylphosphine) palladium (5 mol%), potassium carbonate, dioxane/water, 100 ℃; (h) trifluoromethyl acetic acid, dichloromethane; (i) triethylamine, acetone/water, room temperature.
In a fifth embodiment of the invention, the application of the four-metal Pt rectangular supramolecular complex in identification and/or detection of alkali metal ions and/or alkaline earth metal ions is provided.
In a sixth embodiment of the present invention, a method for identifying and/or detecting sodium ions is provided, wherein the rectangular supramolecular complex of the four metals Pt is added into a solution to be detected to perform fluorescence detection;
wherein the four-metal Pt rectangular supramolecular complex is a compound shown by Pt1,
or, in the preparation method of the four-metal Pt rectangular supermolecule complex, the ligand modified by crown ether is L1The compounds shown.
In a seventh embodiment of the present invention, a method for identifying and/or detecting magnesium ions is provided, wherein the four-metal Pt rectangular supramolecular complex is added to a solution to be detected to perform fluorescence detection;
wherein the four-metal Pt rectangular supramolecular complex is a compound shown by Pt2,
or, in the preparation method of the four-metal Pt rectangular supermolecule complex, the ligand modified by crown ether is L2The compounds shown.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
1. Preparation of organic ligand L1
Synthesis of intermediate 2, 7-dibromo-9, 10-phenanthro 15-crown-5 (2)
A250 mL round bottom flask was charged with 2, 7-dibromophenanthrene-9, 10-quinone (4.25g,11.6mmol), tetrabutylammonium bromide (1.48g,4.6mmol), sodium dithionate (8.20g,47.0mmol), tetrahydrofuran (70mL) and water (70mL) and stirred for 15 min. Then, a tetrahydrofuran solution (10ml) of tetraethyleneglycol p-toluenesulfonate (5.83g,11.6mmol) was added dropwise. Then 20mL of aqueous sodium hydroxide (14.0M) was added. The mixture was stirred under reflux for 15 hours, and the aqueous layer was separated. The aqueous layer was extracted three times with ethyl acetate (50 mL each), the organic phases combined and washed successively with water (3X 50mL), ammonium hydroxide solution (10%, 2X 50mL) and saturated brine (1X 50 mL). The organic phase was dried over anhydrous magnesium sulfate and removed by rotary evaporationThe solvent and the remaining solid were purified by silica gel column chromatography (eluent: petroleum ether/ethyl acetate 2:1 by volume) to obtain 1.30g of a white crystalline solid (yield 21%). Melting point 151 ℃.1H NMR(300MHz,CDCl3,25℃,TMS,ppm):8.43(d,J＝9.0Hz,2H,2ArH)；8.35(s,2H,2ArH)；7.71(d,J＝9.0Hz,2H,2ArH)；4.42(t,J＝6.0Hz,4H,2-CH2-)；4.11(t,J＝6.0Hz,4H,2-CH2-)；3.84-3.79(m,8H,4-CH2-).IR(KBr pellet,cm-1):2930(m)；1614(m)；1597(s)；1471(m)；1437(m)；1130(s)；1069(s)；792(m)。
Synthesis of intermediate 2, 7-bis (4-tert-butoxycarbonylphenyl) -9, 10-phenanthro 15-crown-5 (4)
Under the protection of nitrogen, the 2, 7-dibromo-9, 10-phenanthro 15-crown-5 (intermediate 2) (0.95g,1.8mmol) synthesized in the above step, 4-tert-butoxycarbonyl-phenylboronic acid pinacol ester (intermediate 3) (1.21g,3.97mmol), tetrakis (triphenylphosphine) palladium (104mg,0.09mmol), and anhydrous potassium carbonate (748mg,5.42mmol) were placed in 20mL dioxane and 5mL water, heated to 100 ℃, and reacted overnight while maintaining the temperature. After the reaction, the reaction mixture was cooled to room temperature. Water was added to the reaction solution, followed by extraction with ethyl acetate 3 times, and the resulting organic phases were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The dried organic phase is filtered, the solvent is removed under reduced pressure and further purified by column chromatography on silica gel (petroleum ether/ethyl acetate 2:1 by volume). This gave 1.2g of a pale yellow solid in 62% yield. Melting point: 212 deg.C.1H NMR(300MHz,CDCl3,25℃,TMS,ppm):8.75(d,J＝9.0Hz,2H,2ArH)；8.49(s,2H,2ArH)；8.15(d,J＝6.0Hz,4H)7.92(d,J＝9.0Hz,2H,2ArH)；7.85(d,J＝9.0Hz,4H)；4.49(t,J＝6.0Hz,4H,2-CH2-)；4.15(t,J＝6.0Hz,4H,2-CH2-)；3.87-3.82(m,8H,4-CH2-)；1.65(s,18H,-C(CH3)3).IR(neat):2977(m)；1703(s)；1606(m)；1450(m)；1301(s)；1166(m)；1112(s)；765(w)。
Preparation of organic ligand 4, 4' - (9, 10-phenanthro 15-crown-5-2, 7-diyl) -dibenzoic acid (L1)
The intermediate 4(1.0g,1.38mmol) obtained in the above procedure was dissolved in 15mL of dichloromethane, 0.94mL (6.9mmol) of a solution of tetrafluoroboric acid in diethyl ether was added thereto, and after the addition was completed,stirring was continued for 2 hours at room temperature. Then, ether was added to precipitate, which was filtered and washed with dichloromethane and ether in this order. Vacuum drying at 50 ℃ gave 0.80g of a white solid in 95% yield. Melting point: at 320 ℃.1H NMR(300MHz,DMSO-d6) 8.98(d, J ═ 9.0Hz, 2H); 8.44(s, 2H); 8.12(d, J ═ 9.0Hz, 4H); 8.06(d, 2H); 8.02(d, J ═ 9.0Hz, 4H); 4.38(s, 4H); 4.04(s, 4H); 3.71(m,8H), IR (neat) 2871(s); 1682(s); 1613 (m); 1423 (m); 1308(s); 1134 (m); 1065 (m); 762(w), as shown in fig. 1.
2. Preparation of rectangular supermolecule complex Pt1 of tetrametallic Pt
23mg (0.02mmol) of 1, 8-bis { trans-bis (triethylphosphine) platinum-nitrate } anthracene was dissolved in 5mL of acetone at room temperature, and then an aqueous solution (5mL) of organic ligand L1(12mg,0.02mmol) and sodium hydroxide (1.6mg,0.04mmol) was added dropwise with stirring and stirring continued for 20 minutes. The precipitated pale yellow solid precipitate was filtered and washed to give the rectangular supramolecular complex Pt1 in 98.3% yield.1H NMR(600MHz,CDCl3):10.11(s,2H),8.46(s,4H),8.40(d,8H,J＝7.8Hz),8.22(s,2H),8.02(d,4H,J＝9Hz),7.84(d,8H,J＝8.4Hz),7.68(m,8H),7.60(d,4H,J＝7.8Hz),7.05(m,4H),4.34(t,J＝4.8Hz,8H,2-CH2-)；4.11(t,J＝4.8Hz,8H,2-CH2-)；3.73-3.70(m,16H,4-CH2-),1.70(m,48H,PCH2CH3),1.07(m,72H,PCH2CH3) As shown in fig. 3.31P{1H}NMR(CDCl3,121.4MHz):δ12.2(s,1JPPt＝2855Hz)。
The single crystal molecular formula of Pt1 is as follows: c225H300Cl6O27.50P12Pt6Has a chemical formula of [ Pt ]6(C36H30O9)3(PEt3)12(C14H8)3]·3(CH2Cl2)·0.5H2And O. The structural formula is shown in figure 4. Two binuclear Pt molecular clamps and two rigid dicarboxylic acid ligands modified by crown ether functional groups form a rectangular supermolecule macrocycle through Pt-O coordination bonds. The compound crystallizes in a triclinic system and belongs to the P-1 space group. One isThe unit cell unit contains 1.5 Pt rectangular supermolecules of metal and six Pt (II) metal centers with different coordination environments. Each Pt (II) metal center is bonded to a C atom, a carboxyl O atom and two P atoms on an anthracene atom, and is in [ PtCP ]2O]A planar tetragonal coordination environment. But the Pt-C bonds around the six metal centers (C (1) -Pt (2) ═ 2.026(8), C (14) -Pt (1) ═ 2.009(9), C (69) -Pt (3) ═ 2.020(9), C (82) -Pt (4) ═ 2.023(8), C (95) -Pt (6) ═ 2.022(9),
) Pt — O bond (O (1) -Pt (2) ═ 2.129(6), O (8) -Pt (1) ═ 2.117(6), O (14) -Pt (3) ═ 2.117(6), O (26) -Pt (4) ═ 2.138(6), O (17) a-Pt (5) ═ 2.123(6),
) And Pt — P bonds (P (1) -Pt (1) ═ 2.291(2), P (2) -Pt (1) ═ 2.298(3), P (3) -Pt (2) ═ 2.314(3), P (4) -Pt (2) ═ 2.282(3), P (5) -Pt (3) ═ 2.312(2), P (6) -Pt (3) ═ 2.318(3), P (7) -Pt (4) ═ 2.306(3), P (8) -Pt (4) ═ 2.297(2), P (9) -Pt (6) ═ 2.296(3), P (10) -Pt (6) ═ 2.317(3), P (11) -Pt (5) ═ 2.295(3),
) Is not exactly the same as key length and key angle. The crystal data are shown in attached Table 1.
TABLE 1 crystallographic data for single crystals of Pt1
Example 2
Preparation of ligand L2
Preparation of intermediate 7
Tetraethylene glycol (1.0mL,5.9mmol) was added to 200mL of dry tetrahydrofuran solvent with sodium hydride (0.5g,12.4mmol, 60% w/w in mineral oil) under nitrogen. After stirring for 20 minutes, 2,2 '-bis (bromomethyl) -4, 4' -dibromobiphenyl (2.94g,5.9mmol) was added to the above reaction solution. Reaction 24For an hour, 10% HCl (1.0mL) was added and stirred for 10 minutes. The tetrahydrofuran solvent was removed under reduced pressure and the residue was taken up in 150mL of dichloromethane (containing 10% CH)3OH), and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent: petroleum ether/ethyl acetate 4:1 by volume) to give 2.1g of a white crystalline solid in 67% yield. Melting point 94 ℃.1H NMR(600MHz,CDCl3):7.70(s,2H),7.42(d,2H,J＝8.4Hz),6.94(d,2H,J＝8.4Hz),4.32(dd,4H,J＝81.6Hz,J＝12Hz),3.63-3.37(m,16H).13C NMR(600MHz,CDCl3):139.0,137.4,131.5,130.7,130.2,121.9,70.8,70.8,70.7,70.4,70.2.IR(neat):2860(s)；1585(w)；1464(m)；1353(m)；1295(w)；1247(w)；1198(w),1121(s)；1094(s)；1040(w)。
Preparation of intermediate 8
Under nitrogen protection, (intermediate 7) (1.06g,2.0mmol), 4-tert-butoxycarbonylphenylboronic acid pinacol ester (intermediate 3) (1.34g,4.4mmol), tetrakis (triphenylphosphine) palladium (115mg,0.1mmol), anhydrous potassium carbonate (828mg,6.0mmol) were placed in 20mL dioxane and 5mL water and heated to 100 deg.C and the temperature was maintained for reaction overnight. After the reaction, the reaction mixture was cooled to room temperature. Water was added to the reaction solution, followed by extraction with ethyl acetate 3 times, and the resulting organic phases were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The dried organic phase was filtered, the solvent removed under reduced pressure and further purified by silica gel column chromatography (petroleum ether/ethyl acetate 3:1 by volume) to give 1.0g of a white solid in 69% yield. Melting point: 132 ℃.1H NMR(600MHz,CDCl3):8.08(d,4H,J＝8.4Hz),7.85(s,2H),7.73(d,4H,J＝8.4Hz),7.59(d,2H,J＝8.4Hz),7.25(d,2H,J＝8.4Hz),4.48(dd,4H,J＝78.6Hz,J＝12Hz),3.65-3.43(m,16H).IR(neat):2981(m)；2866(m),1703(s),1606(w),1464(w)；1367(m)；1301(s)；1166(s)；1121(s)；837(w)。
Preparation of organic ligand L2
Intermediate 8(0.96g,1.32mmol) was dissolved in 15mL of dichloromethane at room temperature, and then trifluoroacetic acid (0.94mL,6.9mmol) was added and stirred at room temperature for 7 hours. The progress of the reaction was monitored by TLC. After the reaction is finished, the solvent is removed under reduced pressure and residues are removedThe remaining solid was washed with ether and dried under vacuum at 50 ℃ to give 0.81g of a near-white solid in 100% yield. Melting point: 291 deg.C.1H NMR(600MHz,DMSO-d6) 12.95(br.2h),8.04(d,4H, J equals 8.4Hz),7.87(s,2H),7.86(d,4H, J equals 8.4Hz),7.71(d,2H, J equals 7.8Hz),7.25(d,2H, J equals 8.4Hz),4.33(dd,4H, J equals 78.6Hz, J equals 12Hz),3.52-3.28(m,16H) as shown in fig. 2.
Preparation of rectangular supermolecule complex Pt2 of tetrametallic Pt
23mg (0.02mmol) of 1, 8-bis { trans-bis (triethylphosphine) platinum-nitrate } anthracene are dissolved in 5mL of acetone at room temperature, and an aqueous solution (5mL) of organic ligand L2(12mg,0.02mmol) and triethylamine (10. mu.L, 0.07mmol) is added dropwise with stirring and stirring is continued for 20 minutes. The precipitated pale yellow solid precipitate was filtered and washed and dried to give the rectangular supramolecular complex Pt2 in 95% yield.1H NMR(600MHz,CDCl3):9.99(d,2H,J＝9.0Hz),8.32(dd,8H,J＝4.8Hz,J＝8.4Hz),8.21(s,2H),7.89(s,4H),7.79(d,8H,J＝7.2Hz),7.68(d,4H,J＝6.6Hz),7.59-7.55(m,8H),7.04-6.99(m,8H),4.39-4.22(dd,8H,J＝35Hz,J＝12Hz),3.57-3.31(m,32H),1.70(m,48H,PCH2CH3),1.06(m,72H,PCH2CH3) As shown in fig. 5.31P{1H}NMR(CDCl3,121.4MHz):δ12.3(s,1JPPt2855Hz) as shown in fig. 6.13C NMR (600MHz, CDCl3), d:170.6,142.1,139.7,138.3,137.3,136.9,134.1,132.3,132.0,130.2,129.8,129.7,127.3,126.3,125.6,124.8,121.7,71.0,70.8,70.64,70.61,70.1,14.7,8.1,8.08,8.04, as shown in FIG. 7.
Example 3
The rectangular supramolecular complex Pt1 and the rectangular supramolecular complex Pt2 are respectively prepared into a solution with the concentration of 1.5 multiplied by 10- 5The results of titration with a 10mmol/l acetonitrile solution of an alkali metal or alkaline earth metal in mol/l acetonitrile are shown in FIGS. 8 to 9, where the luminescence signal of Pt1 complex is shown for Na metal+Has stronger response, and the luminescent signal of the Pt2 complex is to metal Mg2+Has stronger response. Shows that the rectangular supermolecule Pt1 can identify the metal Na+Ion, Pt2 rectangular supermolecule capable of recognizing metal Mg2+Ions.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. The crown ether modified ligand is characterized in that the chemical structural formula is shown as L1Or L2As shown in the drawings, the above-described,
2. a preparation method of crown ether modified ligand is characterized by comprising the step of obtaining L by using a compound 1, tetraethyleneglycol p-toluenesulfonate and a compound 3 as raw materials according to the following reaction formula1A process for preparing the ligand compound;
3. a preparation method of crown ether modified ligand is characterized by comprising the step of obtaining L by using a compound 6, tetraethyleneglycol and a compound 3 as raw materials according to the following reaction formula2A process for preparing the ligand compound;
4. the method of claim 2, wherein the compound 2 is prepared by: reacting the compound 1 with tetrabutylammonium bromide and sodium dithionate, and then adding tetraethylene glycol p-toluenesulfonate to react under an alkaline condition.
5. The method of claim 2, wherein the reaction to produce compound 4 is a Suzuki reaction.
6. The method of claim 3, wherein the reaction to prepare compound 7 is a substitution reaction.
7. The method of claim 3, wherein the reaction to produce compound 8 is a Suzuki reaction.
8. A rectangular supermolecular complex of four metals Pt is characterized in that the chemical structural formula is shown as Pt1 or Pt2,
9. the rectangular supramolecular complex of tetrametallic Pt as claimed in claim 8, wherein Pt1 has the single crystal formula C225H300Cl6O27.50P12Pt6Has a chemical formula of [ Pt ]6(C36H30O9)3(PEt3)12(C14H8)3]·3(CH2Cl2)·0.5H2O。
10. The rectangular supramolecular complex of tetrametallic Pt as claimed in claim 9, wherein single crystal of Pt1 is crystallized in the triclinic system, belonging to the P-1 space group, containing 1.5 rectangular supramolecules of metallic Pt in one unit cell, with six divalent Pt metal centers with different coordination environments; each divalent Pt metal center is bonded to a C atom, a carboxyl O atom and two P atoms on an anthracene, and is located in [ PtCP ]2O]A planar tetragonal coordination environment.
11. A preparation method of a rectangular supermolecule complex of four metals Pt is characterized in that the ligand modified by crown ether in claim 1 and a compound 5 are reacted under an alkaline condition to obtain the rectangular supermolecule complex, wherein the molar ratio of the ligand modified by crown ether to the compound 5 is 1: 0.9-1.1;
the structural formula of compound 5 is:
12. use of the rectangular supramolecular complexes of tetrametal Pt according to claim 8 or 9 or obtained by the preparation process according to claim 11 for the identification and/or detection of alkali metal ions and/or alkaline earth metal ions.
13. A method for identifying and/or detecting sodium ions, which is characterized in that the rectangular supramolecular complex of the four metals Pt as claimed in claim 8 or 9 or the rectangular supramolecular complex of the four metals Pt as obtained by the preparation method as claimed in claim 11 is added into a solution to be detected for fluorescence detection;
wherein the four-metal Pt rectangular supramolecular complex is a compound shown by Pt1,
or, in the preparation of rectangular supramolecular complexes of tetrametallic Pt, the preparation of claim 11, wherein the ligand modified with crown ether is L1The compounds shown.
14. A method for identifying and/or detecting magnesium ions, the rectangular supramolecular complex of the four metals Pt as claimed in claim 5 or 6 or the rectangular supramolecular complex of the four metals Pt as obtained by the preparation method as claimed in claim 11 is added into a solution to be detected, and fluorescence detection is carried out;
wherein the four-metal Pt rectangular supramolecular complex is a compound shown by Pt2,
or, in the process for the preparation of rectangular supramolecular complexes of tetrametallic Pt, in the process for the preparation of claim 11, coronaThe ether-modified ligand is L2The compounds shown.
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