CN115746025B - Cyclooctatetrathiophene macrocyclic molecule, and preparation method and application thereof - Google Patents
Cyclooctatetrathiophene macrocyclic molecule, and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 16
- 239000000539 dimer Substances 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 239000013638 trimer Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 66
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 17
- -1 dihydrogen phosphate anion Chemical class 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 150000001450 anions Chemical class 0.000 abstract description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 abstract description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 5
- 238000004448 titration Methods 0.000 description 22
- 238000005481 NMR spectroscopy Methods 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 238000002835 absorbance Methods 0.000 description 17
- 238000010668 complexation reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 6
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 150000002678 macrocyclic compounds Chemical class 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 3
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000012746 preparative thin layer chromatography Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
The application relates to a cyclooctatetrathiophene macrocyclic molecule, a preparation method and application thereof, wherein the cyclooctatetrathiophene macrocyclic molecule has the following components in percentage by weightSuch as COTh-Dimer, COTh-Trimer, COTh-tetra or COTh-Pentamer:wherein,is thatR is any one of hydrogen atom, TMS, C1-C30 alkoxy and C1-C30 alkyl. The cyclooctatetrathiophene macrocyclic molecule is used for identifying anions such as halogen, sulfonate, dihydrogen phosphate and the like.
Description
Technical Field
The application belongs to the technical field of supermolecular chemistry, and particularly relates to a cyclooctatetrathiophene macrocyclic molecule, a preparation method and application thereof.
Background
Anions have important influence on vital activities, the recognition and transportation of anions are necessary for vital activities of human bodies, the anions have positive significance on the vital health of the human bodies, and the anions with high content have destructive effects on the environment. The recognition and transportation of anions are realized, so that the mechanism of human vital activities is known, the pollution problem caused by high-content anions in the environment is solved, and the method has important significance for human health survival. The construction of novel supermolecular macrocyclic structures with anion recognition is a potentially powerful means to solve these problems, and is also a popular field of research in supermolecular chemistry.
The utilization of the pre-assembly of the supermolecule macrocyclic structure, and the increase of the hydrogen bond binding sites of the macrocyclic is an important means for realizing efficient anion recognition. 2, 6-pyridine diamide is a functional group capable of providing hydrogen bond donor and acceptor simultaneously, and introducing the functional group into the construction of a macrocyclic structure can increase the complexing ability and recognition ability of a macrocyclic anion. The octatetrathiophene is a flexible molecule with a three-dimensional saddle-shaped structure, the molecular size is larger than that of a large ring structure which is already reported by benzene rings, alkyl chains and the like, and the large ring structure constructed by the octatetrathiophene has larger cavity size, so that the large guest molecule can be identified. However, the prior art does not realize the synthesis of a macrocyclic molecular structure which can have a plurality of hydrogen bond binding sites, simultaneously serve as a donor and acceptor of hydrogen bonds and has a flexible and large-size cavity and good recognition effect on anions by molecular design and using cyclooctatetrathiophene and 2, 6-pyridine diamide.
Disclosure of Invention
The invention aims to solve the technical problems that: in order to solve the defects that the prior art does not realize the synthesis of a class of macrocyclic molecule with a plurality of hydrogen bond binding sites and simultaneously serving as a donor and acceptor of hydrogen bonds by utilizing the cyclooctatetrathiophene and the 2, 6-pyridine diamide, and has good recognition effect on anions such as halogen, sulfonate, dihydrogen phosphate and the like by using flexible and large-size cavities, the invention provides the cyclooctatetrathiophene macrocyclic molecule, and the preparation method and the application thereof.
The technical scheme adopted for solving the technical problems is as follows:
a cyclooctatetrathiophene macrocyclic molecule having a structure as shown in COTh-Dimer, COTh-primer, COTh-Tetramer or COTh-Pentamer:
wherein,is->R is any one of hydrogen atom, TMS, C1-C30 alkoxy and C1-C30 alkyl.
The invention also provides a preparation method of the cyclooctatetrathiophene macrocyclic molecule, and the reaction formula is as follows:
wherein,is->R is any one of hydrogen atom, TMS, C1-C30 alkoxy and C1-C30 alkyl.
The reaction steps are as follows:
s1: will beAnd->Obtaining +.>
S2: will beUnder the protection of inert gas, adding an organic solvent and triethylamine, then adding a 2, 6-pyridine diacyl chloride solution at the temperature of-5 ℃, and heating to room temperature to react to obtain the octatetrathiophene macrocyclic molecules COTh-Dimer, COTh-Trimer, COTh-Tetramer and COTh-Pentamer.
Preferably, the Suzuki coupling reaction is: will beUnder the protection of inert gas, the tetraphenylphosphine palladium or palladium acetate and carbonate are added with an organic solvent and water for heating reaction.
Preferably, the temperature of the heating reaction is 60 to 100 ℃.
Preferably, the molar ratio of the organic solvent to water is preferably 5-15:1.
Preferably, the saidThe molar ratio of the tetraphenylphosphine palladium or the palladium acetate to the carbonate is 0.3-0.5:0.7-1:0.3-0.5:1.8-2.2.
Preferably, the preparation method of the 2, 6-pyridine diacid chloride solution comprises the following steps: adding an organic solvent into 2, 6-pyridine diacid chloride under the protection of inert gas to prepare 2, 6-pyridine diacid chloride solution, wherein the 2, 6-pyridine diacid chloride solution is prepared byThe concentration ratio of the concentration of the added organic solvent and triethylamine to the concentration of the 2, 6-pyridine diacyl chloride solution is preferably 1:6-10, and the +.>The volume ratio of the organic solvent and the triethylamine is preferably 110-130:0.1.
Preferably, the 2, 6-pyridine diacid chloride solution is added dropwise.
Preferably, in the step S2, a 2, 6-pyridine diacyl chloride solution is added under ice water bath conditions.
Preferably, the organic solvent is at least one of dichloromethane, tetrahydrofuran, diethyl ether, toluene and chloroform.
The invention also provides application of the cyclooctatetrathiophene macrocyclic molecule in halogen or dihydrogen phosphate anion recognition.
The beneficial effects of the invention are as follows:
the invention provides four kinds of ring octatetrathiophene macrocyclic molecules with brand new structures and a preparation method thereof, four kinds of ring octatetrathiophene macrocyclic structures are obtained simultaneously with high yield by a one-step method, and the recognition processes of the four kinds of ring octatetrathiophene macrocyclic molecules on anions such as halogen, sulfonate, dihydrogen phosphate and the like are studied, so that the four kinds of ring octatetrathiophene macrocyclic molecules have good recognition effects on the anions such as halogen, sulfonate, dihydrogen phosphate and the like, particularly have stronger recognition effects on fluoride ions, the complexation capability of the four kinds of ring octatetrathiophene macrocyclic molecules with four kinds of structures on the same anions is also different, and the generated reasons are due to the difference of cavity sizes of the four kinds of ring octatetrathiophene macrocyclic molecules and the difference of the number of hydrogen bond donors contained in the ring octatetrathiophene macrocyclic molecules with four kinds of structures.
Drawings
FIG. 1 shows COTh-2PhNH obtained in example 1 of the present invention 2 -1 nuclear magnetic resonance hydrogen profile;
FIG. 2 is a COTh-2PhNH obtained in example 1 of the present invention 2 -1 nuclear magnetic resonance carbon spectrum;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of COTh-Dimer-1 prepared by the invention;
FIG. 4 is a nuclear magnetic resonance carbon spectrum of COTh-Dimer-1 prepared by the present invention;
FIG. 5 is a mass spectrum of COTh-Dimer-1 prepared by the invention;
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of COTh-Trimer-1 prepared by the invention;
FIG. 7 is a nuclear magnetic resonance carbon spectrum of COTh-Trimer-1 prepared by the invention;
FIG. 8 is a mass spectrum of COTh-Trimer-1 prepared by the invention;
FIG. 9 is a mass spectrum of COTh-tetra-1 prepared by the present invention;
FIG. 10 is a mass spectrum of COTh-Pentamer-1 prepared by the present invention;
FIG. 11 is a nuclear magnetic titration spectrum of COTh-Dimer-1 prepared in the present invention with fluoride ion added in equivalent;
FIG. 12 is a nuclear magnetic titration spectrum of COTh-Trimer-1 prepared by the invention with fluoride ion added in equivalent;
FIG. 13 is a nuclear magnetic titration spectrum of COTh-Dimer prepared in accordance with the present invention with chloride ion addition in equivalent amounts;
FIG. 14 is a nuclear magnetic titration spectrum of COTh-Trimer-1 prepared in the present invention with chloride ion added in equivalent;
FIG. 15 is a nuclear magnetic titration spectrum of COTh-Dimer-1 prepared in the present invention with the addition of bromide in equivalent amounts;
FIG. 16 is a nuclear magnetic titration spectrum of COTh-Trimer prepared in the present invention with the addition of bromide in equivalent amounts;
FIG. 17 is a nuclear magnetic titration spectrum of COTh-Dimer-1 prepared in accordance with the present invention with the addition of iodide ion in equivalent amounts;
FIG. 18 is a nuclear magnetic titration spectrum of COTh-Trimer-1 prepared in the present invention with iodine ion added in equivalent;
FIG. 19 shows the COTh-Dimer-1 produced by the present invention with H 2 PO 4 - Adding the nuclear magnetic titration spectrograms in a equivalent way;
FIG. 20 shows the COTh-Trimer-1 with H prepared by the present invention 2 PO 4 - By adding in equivalentNuclear magnetic titration spectrograms of (2);
FIG. 21 is a graph of UV titration data for COTh-tetra-1 as chloride ions are added in equivalent amounts;
FIG. 22 is a graph of UV titration data for COTh-tetra-1 as bromide is added in equivalent amounts;
FIG. 23 is a graph of UV titration data for COTh-tetra-1 as iodide ions are added in equivalent increments;
FIG. 24 is a graph of UV titration data for COTh-Pentamer-1 with chloride ion addition in equivalent amounts;
FIG. 25 is a graph of UV titration data for COTh-Pentamer-1 with the addition of bromide in equivalent amounts;
FIG. 26 is a graph of UV titration data for COTh-Pentamer-1 with the addition of iodide ion in equivalent amounts;
FIG. 27, left panel (a) shows COTh-Dimer-1 and Cl - The absorbance at different ratios, right panel (b) is COTh-Dimer-1 at 338nm with Cl - Job's plot operating curve of (2);
FIG. 28, left panel (a) shows COTh-Dimer-1 and Br - The absorbance at different ratios, right panel (b) is COTh-Dimer-1 and Br at 338nm - Job's plot operating curve of (2);
FIG. 29, left panel (a) shows COTh-Dimer-1 and I - The absorbance at different ratios, right panel (b) is COTh-Dimer-1 at 338nm and I - Job's plot operating curve of (2);
FIG. 30, left panel (a), shows COTh-Trimer-1 and Cl - The absorbance at different ratios, right panel (b) is COTh-Trimer-1 and Cl at 353nm - Job's plot operating curve of (2);
FIG. 31, left panel (a), shows COTh-Trimer-1 and Br - The absorbance at different ratios, right panel (b) is COTh-Trimer-1 and Cl at 353nm - Job's plot operating curve of (2);
FIG. 32, left panel (a), shows COTh-Trimer-1 and I - The absorbance at different ratios, right panel (b) is COTh-Trimer-1 and Cl at 353nm - Job's plot operating curve of (2);
FIG. 33, left panel (a) shows COTh-Tetramer-1 and Cl - The absorption at different ratios, right (b) is COTh-Tetramer-1 at 350nm with Cl - Job's plot operating curve of (2);
FIG. 34, left panel (a) shows COTh-Tetramer-1 and Br - The absorption at different ratios, right (b) is COTh-Tetramer-1 at 350nm with Cl - Job's plot operating curve of (2);
FIG. 35, left panel (a) shows COTh-Tetramer-1 and I - The absorption at different ratios, right (b) is COTh-Tetramer-1 at 350nm with Cl - Job's plot operating curve of (2);
FIG. 36, left panel (a) shows COTh-Peantmer-1 and Cl - The absorption at different ratios, right (b) is COTh-Peantmer-1 and Cl at 350nm - Job's plot operating curve of (2);
FIG. 37 left panel (a) shows COTh-Peantmer-1 and Br - The absorption at different ratios, right (b) is COTh-Peantmer-1 and Cl at 350nm - Job's plot operating curve of (2);
FIG. 38 left panel (a) shows COTh-Peantmer-1 and I - The absorption at different ratios, right (b) is COTh-Peantmer-1 and Cl at 350nm - Job's plot operating curve of (c).
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other.
The technical solutions of the present application will be described in detail below with reference to the accompanying drawings in combination with embodiments.
Example 1
The example provides a method for preparing a cyclooctatetrathiophene macrocyclic molecule, the reaction formula is as follows:
wherein,is->
The reaction steps are as follows:
S1:(COTh-2PhNH 2 -synthesis of 1): will->(COTh-2Br-1)(250mg,0.40mmol)、/>(191 mg,0.87 mmol), palladium tetraphenylphosphine (37 mg,0.40 mmol), potassium carbonate (274 mg,1.98 mmol) were added to a 100mL schlenk flask, oxygen (30 min) was removed by vacuum, 40mL of anaerobic Tetrahydrofuran (THF) and 4mL of anaerobic water were added under argon protection, the reaction was carried out in an oil bath at 80 ℃ for 16 hours, after completion of the reaction and cooling to room temperature, the reaction solvent was removed by swirling, 50mL of Dichloromethane (DCM) was added to dissolve and transferred to a separating funnel, water (3 x 50 mL) was added to wash, the aqueous phase was extracted with (3 x 100 mL) DCM, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, the solvent was removed by swirling, and separated using column chromatography (silica gel 300-400 mesh, DCM: pe=3:1) to give a yellow solid COTh-2PhNH 2 -1:236mg, yield: 90%;
COTh-2PhNH 2 -1：M.p.>300℃，IR(KBr):3379,3213,2954,1617,1517,1286,1252,1007,985,835,760cm -1 ， 1 H NMR(400MHz,DMSO-d 6 )δ7.34(d,J＝8.6Hz,4H),7.28(s,2H),7.22(s,2H),6.58(d,J＝8.6Hz,4H),5.42(s,4H),0.32(s,18H)， 13 C NMR(101MHz,DMSO)δ149.25,146.64,141.88,137.73,137.42,136.98,136.73,126.97,126.40,123.43,120.42,113.93,-0.34，HRMS(MALAI)m/z calcd for[C34H34N2S4Si2]654.1138,found 654.1147(Error:1.47ppm)；
s2, synthesis of COTh-Dimer-1, COTh-Trimer-1, COTh-tetra-1 and COTh-Pentamer-1: the COTh-2PhNH prepared in the step S1 is processed 2 1 (56 mg,0.085 mmol) was added to a 250mL Schlenk flask, dried under vacuum for 30min, and under argon, 120mL freshly distilled DCM, 0.1mL freshly distilled Triethylamine (TEA) were added; 2, 6-Pyridinedichloride (17 mg,0.085 mmol) was added to another 25mL Schlenk flask, dried under vacuum for 30min, and 15mL freshly distilled DCM was added under argon to prepare 2, 6-Pyridinedichloride solution; will 25Placing a 0mL Schlenk bottle in an ice water bath, and slowly dripping 2, 6-pyridine diacyl chloride solution into the mixture containing COTh-2PhNH by using a dry syringe under the protection of argon 2 In a 250mL Schlenk flask of-1, after the completion of the dropwise addition, the mixture was slowly warmed to room temperature and reacted for 16 hours. After the reaction was completed, the reaction mixture was transferred to a 250mL separating funnel, washed with saturated brine (3×100 mL), the aqueous phase was extracted with (3×100 mL) DCM, the organic phases were combined and dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by spin-on, and separated using preparative thin layer chromatography (DCM-DCM: CH 3 Oh=75:1) to give a yellow solid, COTh-oligomer-1:20 mg, yield: 29%; COTh-Trimer-1:27mg, yield: 39%; COTh-Tetramer-1:2mg, yield: 3%; compound COTh-Pentamer-1:2mg, yield: 3%.
COTh-Dimer-1：M.p.>300℃，IR(KBr):2966,2892,1682,1587,1529,1411,1251,1048,1008,989,838,756cm -1 ， 1 H NMR(400MHz,Chloroform-d)δ9.49(s,4H),8.49(d,J＝7.8Hz,4H),8.18(s,2H),7.68(d,J＝8.3Hz,8H),7.57(d,J＝8.2Hz,8H),7.15(s,4H),7.11(s,4H),0.36(s,36H)， 13 C NMR(126MHz,Chloroform-d)δ161.14,149.03,145.16,142.92,140.06,138.62,137.85,137.36,136.66,136.42,131.95,131.32,127.31,126.30,125.73,121.34,0.02.HRMS(MALDI)m/z calcd for[C82H70N6O4Si4S8]1570.2354,found 1570.2296(Error:3.71ppm)。
COTh-Trimer-1:M.p.>300℃，IR(KBr):2926,2839,1685,1587,1526,1409,1249,1008,988,837,756cm -1 ， 1 H NMR(400MHz,Chloroform-d)δ9.57(s,2H),8.52(d,J＝7.7Hz,6H),8.15(t,J＝7.8Hz,3H),7.81(s,12H),7.66(d,J＝8.5Hz,12H),7.22(s,6H),7.13(s,6H),0.36(s,53H)， 13 C NMR(126MHz,Chloroform-d)δ160.92,148.71,144.78,142.81,139.68,138.19,137.75,137.18,136.82,131.21,130.28,126.20,125.49,120.18,0.05，HRMS(MALDI)m/z calcd for [C 123 H 105 N 9 O 6 Si 6 S 12 ]2355.3542,found 2355.3446(Error:4.07ppm)。
COTh-Tetramer-1:M.p.>300℃.IR(KBr):2968,1685,1514,1250,835cm -1 . 1 H NMR(400MHz,THF-d 8 )δ10.33(s,8H),8.47(d,J＝7.7Hz,8H),8.21(t,J＝7.8Hz,4H),7.93(d,J＝8.7Hz,16H),7.68(d,J＝8.7Hz,16H),7.33(s,8H),7.24(s,8H),0.34(s,72H). 13 C NMR(126MHz,THF-d 8 )δ162.22,150.50,146.16,143.34,140.37,139.34,139.24,138.72,138.33,137.90,131.75,130.76,126.72,126.68,126.26,121.90.MALDI-TOF HRMS(HCCA)m/z calcd for[C 164 H 140 N 12 O 8 Si 8 S 16 Na]3163.46445,found 3163.44947(Error:4.37ppm).
COTh-Pentamer-1:M.p.>300℃.IR(KBr):2955,1685,1525,1243,841cm -1 . 1 H NMR(400MHz,THF-d 8 )δ10.33(s,10H),8.47(d,J＝7.8Hz,10H),8.22((t,J＝7.8Hz,5H),7.94(d,J＝8.6Hz,20H),7.68(d,J＝8.6Hz,20H),7.34(s,10H),7.24(s,10H),0.34(s,90H). 13 C NMR(126MHz,THF-d 8 )δ162.22,150.50,146.17,143.34,140.37,139.35,139.24,138.72,138.33,137.90,131.75,130.76,126.69,126.26,121.90.HRMS(MALDI)m/z calcd for[C 205 H 176 N 15 O 10 Si 10 S 20 ]3926.5826,found 3926.5902(Error:-1.9ppm)。
Example 2
The example provides a method for preparing a cyclooctatetrathiophene macrocyclic molecule, the reaction formula is as follows:
wherein,is->
The reaction steps are as follows:
S1:(COTh-2PhNH 2 -2) synthesis: will->(COTh-2Br-2)(150mg,0.31mmol)、/>(149 mg,0.68 mmol), palladium acetate (5.54 mg,0.24 mmol), potassium carbonate (213 mg,1.54 mmol) were added to a 100mL schlenk flask, oxygen (30 min) was removed under vacuum, 40mL of anaerobic Tetrahydrofuran (THF) and 5mL of anaerobic water were added under argon protection, the reaction was carried out in an oil bath at 60 ℃ for 36 hours, after completion of the reaction and cooling to room temperature, the reaction solvent was removed by swirling, 100mL of Dichloromethane (DCM) was added to dissolve and transferred to a separating funnel, water (3 x 100 mL) was added to wash, the aqueous phase was extracted with (3 x 150 mL) DCM, the organic phase was combined, dried over anhydrous magnesium sulfate, filtered, the solvent was removed by swirling, and isolated using column chromatography (silica gel 300-400 mesh, DCM: pe=5:1) to give a yellow solid COTh-2PhNH 2 -2:135mg, yield: 86%;
s2, synthesis of COTh-Dimer-2, COTh-Trimer-2, COTh-tetra-2 and COTh-Pentamer-2: the COTh-2PhNH prepared in the step S1 is processed 2 2 (100 mg,0.20 mmol) was added to a 5000mL Schlenk flask, dried under vacuum for 30min, and 250mL freshly distilled DCM, 0.3mL freshly distilled Triethylamine (TEA) were added under argon; 2, 6-Pyridinedichloride (40 mg,0.20 mmol) was added to another 50mL Schlenk flask, dried under vacuum for 30min, and 25mL freshly distilled DCM was added under argon to prepare 2, 6-Pyridinedichloride solution; placing 500mL Schlenk bottle in ice water bath, and slowly dripping 2, 6-pyridine diacid chloride solution into the mixture containing COTh-2PhNH by using a dry syringe under the protection of argon 2 In a 500mL Schlenk flask of-2, after the completion of the dropwise addition, the mixture was slowly warmed to room temperature and reacted for 16 hours. After the reaction was completed, the reaction mixture was transferred to a 500mL separating funnel, washed with saturated brine (3×200 mL), the aqueous phase was extracted with (3×200 mL) DCM, the organic phases were combined and dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by spin-on, and separated using preparative thin layer chromatography (DCM-DCM: CH 3 Oh=55:1) to give a yellow solid, COTh-oligomer-2:36 mg, yield: 26%; COTh-Trimer-2:44mg, yield: 35%; COTh-Tetramer-2:4mg, yield: 3%; compound COTh-Pentamer-2:5mg, yield: 4%.
Effect example 1 Nuclear magnetic titration experiment of Cyclooctatetrathiophene macrocyclic molecules
Test example 1 preparation of COTh-Dimer-1,Recognition of different halogen ions and dihydrogen phosphate ions by COTh-Trimer-1, COTh-tetra-mer-1, COTh-Pentamer-1, respectively, halogen ions being provided by tetra-n-butyl ammonium fluoride (TBAF), tetra-n-butyl ammonium chloride (TBACl), tetra-n-butyl ammonium bromide (TBABr) and tetra-n-butyl ammonium iodide (TBAI), dihydrogen phosphate ions being provided by TBAH 2 PO 4 Providing.
According to the effect example, nuclear magnetic titration is firstly carried out on two kinds of cyclic octatetrathiophene macrocyclic molecules, namely COTh-Dimer-1 and COTh-Trimer-1, along with the continuous increase of the concentration of halogen ions by a nuclear magnetic resonance hydrogen spectrometer, and the test conditions are as follows: nuclear magnetic titration experimental instrument: nuclear magnetic resonance hydrogen spectrometer (Bruker, AVANCE 400 MHz); COTh-Dimer-1, COTh-Trimer-1, TBAF, TBACl, TBABr, TBAI, TBAH 2 PO 4 The solvents used were all deuterated chloroform (CDCl) 3 ) The concentration of the two kinds of octatetrathiophene macrocyclic molecules is 1mmol/L, TBAF, TBACl, TBABr, TBAI, TBAH 2 PO 4 The concentration of (2) is 200mmol/L; temperature: 298K. According to nuclear magnetic resonance experimental spectrograms (fig. 11-18), the change of the amide hydrogen of the octatetrathiophene macrocyclic molecule along with the addition of anions is most remarkable, the H … F bond formed by the octatetrathiophene macrocyclic molecule and fluorine ions and the amide hydrogen in all halogen ions is widened due to the very strong hydrogen bond acting force, no obvious peak signal is generated in the spectrograms, so that the COTh-Dimer-1 and COTh-Trimer-1 two octathiophene macrocyclic molecules and the para-fluorine ions form very strong recognition acting force, and according to the change degree of the chemical displacement caused by the action of different anions and the amide hydrogen in the macrocycle, the change of the four halogen ions along with the cycle leads to the increase of the atomic radius, so that the hydrogen bond acting force is reduced, and other anions such as chloride ions, bromide ions, iodide ions and dihydrogen phosphate show the same change trend, which shows that a host-guest complex is formed with the macrocyclic structure, so that the macrocycle has the capability of recognizing the anions.
The effect example also carries out ultraviolet titration on two kinds of octatetrathiophene macrocyclic molecules of COTh-Tetramer-1 and COTh-Pentamer-1 by an ultraviolet-visible spectrophotometer, and the test conditions are as follows: ultraviolet visible spectrophotometer(SHIMADZU UV-1900): the solvents used in COTh-Tetramer-1 and COTh-peatment-1 and TBACl, TBABr, TBAI were all spectroscopically pure Tetrahydrofuran (THF), and the concentrations of the two octatetrathiophene macrocyclic molecules were 3X 10 -6 mol/L，TBACl、TBABr、TBAI、TBAH 2 PO 4 The concentration of (2) is 3×10 -3 mol/L, temperature: 298K. The UV-Vis titration spectra (FIGS. 21-26) showed a significant change in absorbance as anions were added, with increasing concentrations of COTh-Tetramer-1, COTh-Peantmer-1, progressively decreasing absorbance, indicating complexation of the compounds COTh-Tetramer-1, COTh-Peantmer-1 with the added anions.
In addition, the four kinds of octatetrathiophene macrocyclic molecules have good recognition effects on halogen anions and other anions (such as sulfonate, dihydrogen phosphate and the like), and nuclear magnetic titration is performed on COTh-Dimer-1 and COTh-Trimer-1 two kinds of octatetrathiophene macrocyclic molecules along with the continuous increase of the concentration of dihydrogen phosphate by a nuclear magnetic resonance hydrogen spectrometer under the following test conditions: nuclear magnetic resonance hydrogen spectrometer (Bruker, AVANCE 400 MHz); COTh-Dimer-1, COTh-Trimer-1, TBAH 2 PO 4 The solvents used were all deuterated chloroform (CDCl) 3 ) The concentration of the two kinds of octatetrathiophene macrocyclic molecules is 1mmol/L, TBAH 2 PO 4 The concentrations of (C) were 200mmol/L, and the results are shown in FIGS. 19-20.
In addition, the first-order complexation constant K of four kinds of cyclic octatetrathiophene macrocyclic molecules of COTh-Dimer-1, COTh-Trimer-1, COTh-Tetramer-1 and COTh-Peantmer-1 to different halogen ions is obtained through calculation 1 Second order complexation constant K 2 The test data are shown in tables 1 and 2, and the result analysis of the test data can obtain that four kinds of octatetrathiophene macrocyclic molecules have very strong complexing force on chloride ions, and the complexing ability is weakened along with the increase of the size of anions; the increase of the number of structural units in the COTh-Tetramer-1 and the COTh-peantimer-1 increases the flexibility of the macrocyclic ring, and the cavity structure formed by the macrocyclic ring is more suitable for chloride ions, so that the complexation constant of the macrocyclic ring is increased. As a result of the analysis, when the host-guest ratio is 1:1, the error is smaller, so the complexation ratio of four kinds of macrocycles and different anions is1:1。
TABLE 1
TABLE 2
Effect example 2Job' plot experiment
To further confirm the complexing ratio of the cyclooctatetrathiophene macrocyclic molecule to the anion, a Job' plot experiment was performed. The experimental method comprises the following steps: the compound COTh-Dimer-1 and COTh-Trimer-1 are accurately weighed respectively, and prepared into 1×10 with spectrally pure dichloromethane -3 M mother liquor, and further diluted to 1X 10 -5 M solution to be measured. After the guest molecules are accurately weighed, the guest molecules are prepared into 1X 10 by using spectroscopically pure dichloromethane -3 M mother liquor, and further diluted to 1X 10 -5 M solution to be measured. The total concentration of the compounds COTh-Dimer-1, COTh-Trimer-1 and guest molecule is controlled to be 1×10 -5 The proportion of M is 1/9,2/8,3/7,4/6,5/5,6/4,7/3,8/2,9/1. The compound COTh-Tetramer-1 and COTh-peatment-1 were accurately weighed and prepared into 1X 10 with spectrally pure tetrahydrofuran -4 M mother liquor, and further diluted to 1X 10 -5 M solution to be measured. The guest molecule is accurately weighed and prepared into 1X 10 by using spectroscopically pure tetrahydrofuran -3 M mother liquor, and further diluted to 1X 10 -5 M solution to be measured. The total concentration of the compound COTh-Tetramer-1, COTh-Peantmer-1 and the guest molecule was controlled to be 3X 10 -6 The proportion of M is 1/9,2/8,3/7,4/6,5/5,6/4,7/3,8/2,9/1. And respectively detecting the UV-Vis absorption spectrograms of each group of samples, and plotting the absorbance difference between the absorbance at a certain wavelength and the absorbance of the compounds COTh-Dimer-1, COTh-Trimer-1, COTh-tetra-1 and COTh-Peantmer-1 against the host-guest ratio to obtain a Job' splot working curve.
Compound COTh-Dimer-1 (H) and Cl - (G) The absorption diagram of the different ratios of (a) is shown in fig. 27 (solvent:dichloromethane, concentration: [ H ]]+[G]＝1×10 -5 M) with Cl - The absorbance value is continuously decreased by increasing the proportion. Delta A is the difference in absorbance change at 338nm (COTh-Dimer-1 vs. Cl at different ratios - Absorbance of the complex was measured to be 1X 10 only -5 Difference in absorbance of the M compound COTh-Dimer-1) and the molar fraction of COTh-Dimer-1 (molefraction= [ H)]/([H]+[G]) A) and plotting the mole fraction of COTh-oligomer-1 to yield the Job' plot operating curve b as shown in fig. 27. Extreme values were obtained when the mole fraction of COTh-Dimer-1 was 0.5, indicating that the compound COTh-Dimer-1 was found to be Cl - The ratio of complex is 1:1, which is consistent with our results deduced from the complex constant calculation. Also, referring to the above experimental method, the compounds COTh-Dimer-1 and Br - 、I - Absorption diagram (solvent: dichloromethane, concentration: [ H ]) at different ratios]+[G]＝1×10 -5 M) and Job' plot as shown in FIGS. 28 and 29, it is evident that the absorption reached an extreme value at a molar ratio of 0.5, proving that the compounds COTh-Dimer-1 and Br - 、I - The complexation ratio was 1:1, consistent with the results deduced from the complexation constant calculation.
Compound COTh-Trimer-1 (H) and Cl - (G) The absorption patterns of the different ratios of (a) are shown in FIG. 30 (solvent: dichloromethane, concentration: [ H ]]+[G]＝1×10 -5 M), adopting the same calculation mode, calculating to obtain the mole fraction of delta A to COTh-Dimer-1 by taking absorbance change at 353nm, and plotting to obtain a Job' plot working curve as shown in b of figure 30. Extreme values were obtained when the mole fraction was 0.5, indicating that the compounds COTh-Trimer-1 and Cl - The ratio of complex was 1:1, consistent with the results deduced from the calculation of the complex constant. COTh-Trimer-1 and Br - 、I - Absorption diagram (solvent: dichloromethane, concentration: [ H ]) at different ratios]+[G]＝1×10 -5 M) and Job' plot curves as shown in FIGS. 31 and 32, the calculated results were similarly 1:1, and they were consistent with the results estimated by the complex constant calculation.
Compound COTh-Tetramer-1 (H) and Cl - (G) The absorption patterns of the different ratios of (a) are shown in FIG. 33 (solvent: tetrahydrofuran, concentration: [ H ]]+[G]＝3×10 -6 M) adopts the same calculation mode to obtain 350
The absorbance at nm was calculated to give a Job' plot as in FIG. 33 b, with an extremum of 0.5, therefore COTh-Tetramer-1 vs. Cl - Also in a 1:1 complexation. Compounds COTh-Tetramer-1 and Br - 、I - Is shown in the formula (solvent: tetrahydrofuran, concentration: [ H.)]+[G]＝3×10 -6 M) and Job' plot as shown in FIGS. 34 and 35, the results showed 1:1 complexation, which both agree with the results deduced from the complexation constant calculation.
Compound COTh-Peantmer-1 (H) and Cl - (G) The absorption patterns of different ratios of (a) and Job' plot working curves are shown in FIG. 36 (solvent: tetrahydrofuran, concentration: [ H ]]+[G]＝3×10 -6 M) whose extreme value of variation is 0.5, so that COTh-Peantmer-1 and Cl - Also in a 1:1 complexation. The compounds COTh-Peantmer-1 and Br were obtained in the same manner - 、I - Is shown in the formula (solvent: tetrahydrofuran, concentration: [ H.)]+[G]＝3×10 -6 M) and Job' plot as shown in FIGS. 37 and 38, the results showed 1:1 complexation, which both agree with the results deduced from the complexation constant calculation.
In conclusion, the Job graph of Job' plot shows that the complexation ratio of four macrocyclic compounds to three halogen ions is 1:1, the number of structural units is increased without changing the complexation number of macrocyclic compounds to anions, and the phenomenon that the four macrocyclic structures are distorted and folded in a solution state is related to the semi-flexible structure of the octatetrathiophene. By analyzing the complex constant table, the macrocyclic pair of three anions Cl can be found - 、Br - 、I - The complexation constant of (c) gradually decreases due to the increasing size of the three halogen ions. For the same halogen ion, as the macrocyclic structure increases, its complexing ability increases, resulting from an increase in the number of intramolecular lactam bonds, leading to an increase in molecular hydrogen bonds.
With the above-described preferred embodiments according to the present application as a teaching, the related workers can make various changes and modifications without departing from the scope of the technical idea of the present application. The technical scope of the present application is not limited to the contents of the specification, and must be determined according to the scope of claims.
Claims (13)
1. A cyclic octatetrathiophene macrocyclic molecule having a structure as shown in COTh-Dimer, COTh-primer, COTh-Tetramer or COTh-Pentamer:
wherein,is->R is any one of hydrogen atom, TMS, C1-C30 alkoxy and C1-C30 alkyl.
2. The method for preparing the cyclooctatetrathiophene macrocyclic molecule according to claim 1, wherein the reaction steps are as follows:
s1: will beAnd->Obtaining +.>
S2: will beUnder the protection of inert gas, adding organic solvent and triethylamine, then adding 2,6 at-5 deg.C-pyridine diacid chloride solution, and raising the temperature to react to obtain the octatetrathiophene macrocyclic molecules COTh-Dimer, COTh-Trimer, COTh-tetra mer and COTh-Pentamer as defined in claim 1.
3. The method for preparing a cyclooctatetrathiophene macrocyclic molecule according to claim 2, wherein the Suzuki coupling reaction is: will beUnder the protection of inert gas, the tetraphenylphosphine palladium or palladium acetate and carbonate are added with an organic solvent and water for heating reaction.
4. The method for producing a cyclooctatetrathiophene macrocyclic molecule according to claim 3, wherein the heating reaction temperature is 60 to 100 ℃.
5. The method for producing a cyclooctatetrathiophene macrocyclic molecule according to claim 3, wherein the molar ratio of the organic solvent to water is 5 to 15:1.
6. The method for producing a cyclooctatetrathiophene macrocyclic molecule according to any one of claims 3 to 5, wherein theThe molar ratio of the tetraphenylphosphine palladium or the palladium acetate to the carbonate is 0.3-0.5:0.7-1:0.3-0.5:1.8-2.2.
7. The method for preparing a cyclooctatetrathiophene macrocyclic molecule according to any one of claims 2 to 5, wherein the preparation method of the 2, 6-pyridine diacid chloride solution is as follows: and adding an organic solvent into the 2, 6-pyridine diacid chloride under the protection of inert gas to prepare a 2, 6-pyridine diacid chloride solution.
8. A process for the preparation of a cyclooctatetrathiophene macrocyclic molecule according to any of claims 2 to 5, whichCharacterized in that the saidThe concentration ratio of the organic solvent and the triethylamine to the 2, 6-pyridine diacyl chloride solution is 1:6-10.
9. The method for producing a cyclooctatetrathiophene macrocyclic molecule according to any one of claims 2 to 5, wherein aThe volume ratio of the organic solvent to the triethylamine is 110-130:0.1.
10. The method for producing a cyclooctatetrathiophene macrocyclic molecule according to any one of claims 2 to 5, wherein the addition condition of the 2, 6-pyridine diacid chloride solution is dropwise addition.
11. The method for producing a cyclooctatetrathiophene macrocyclic molecule according to any one of claims 2 to 5, wherein in step S2, a 2, 6-pyridine diacid chloride solution is added under ice water bath conditions.
12. The method for producing a cyclooctatetrathiophene macrocyclic molecule according to any one of claims 2 to 5, wherein the organic solvent is at least one of dichloromethane, tetrahydrofuran, diethyl ether, toluene, and chloroform.
13. Use of a cyclooctatetrathiophene macrocyclic molecule according to claim 1 for halogen or dihydrogen phosphate anion recognition.
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