CN117736216B - Trfoster's Base framework macrocyclic compound and preparation method and application thereof - Google Patents
Trfoster's Base framework macrocyclic compound and preparation method and application thereof Download PDFInfo
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- 150000002678 macrocyclic compounds Chemical class 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000012074 organic phase Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 229940125782 compound 2 Drugs 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 6
- 150000007517 lewis acids Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- SQTUYFKNCCBFRR-UHFFFAOYSA-N (2,4-dimethoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C(OC)=C1 SQTUYFKNCCBFRR-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 238000005580 one pot reaction Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 238000010791 quenching Methods 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- 238000010668 complexation reaction Methods 0.000 abstract description 9
- -1 Tr-ger's Base skeleton macrocyclic compound Chemical class 0.000 abstract description 8
- 230000007812 deficiency Effects 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- SXPSZIHEWFTLEQ-UHFFFAOYSA-N tröger's base Chemical compound C12=CC=C(C)C=C2CN2C3=CC=C(C)C=C3CN1C2 SXPSZIHEWFTLEQ-UHFFFAOYSA-N 0.000 abstract 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 12
- 241001120493 Arene Species 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 229940126214 compound 3 Drugs 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- QOZLFNQLIKOGDR-UHFFFAOYSA-N (2,5-dimethoxyphenyl)boronic acid Chemical compound COC1=CC=C(OC)C(B(O)O)=C1 QOZLFNQLIKOGDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001296 phosphorescence spectrum Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ROEQGIFOWRQYHD-UHFFFAOYSA-N (2-methoxyphenyl)boronic acid Chemical compound COC1=CC=CC=C1B(O)O ROEQGIFOWRQYHD-UHFFFAOYSA-N 0.000 description 1
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SGLGUTWNGVJXPP-UHFFFAOYSA-N benzene-1,3,5-tricarbonitrile Chemical compound N#CC1=CC(C#N)=CC(C#N)=C1 SGLGUTWNGVJXPP-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of organic synthetic chemistry, and particularly relates to a Tr-ger's Base skeleton macrocyclic compound, a preparation method and application thereof, wherein the Tr-ger's Base skeleton macrocyclic compound contains a reverse V-shaped Tr-ger's Base chiral functional skeleton and presents a molecular box-shaped three-dimensional topological structure, the macrocyclic compound structure is shown as a formula I or a formula II, and the structures shown as the formula I or the formula II both contain meso and raceme. The Tr foster's Base macrocyclic molecule provided by the invention can realize extremely strong complexation of BTCN molecules with neutral electron deficiency in an organic solvent due to the matching property of the cavity size and the electrical property, and the complexation constant is as high as 10 4 M‑1, which is difficult to realize by complexation of BTCN in an organic phase of the traditional macrocyclic molecule.
Description
Technical Field
The invention belongs to the field of organic synthetic chemistry, and particularly relates to a Tr ringer's Base skeleton macrocyclic compound, and a preparation method and application thereof.
Background
Macrocyclic synthetic hosts are the main tools for supramolecular chemistry research. Classical macrocycles such as cyclodextrins, calixarenes, cucurbiturils, and column arenes are widely used in the fields of chemistry, biology, materials, and the like due to their rigid cavity structure and excellent molecular recognition properties. Macrocyclic arene is an important macrocyclic compound, which is a ring molecule formed by connecting an alkoxy substituted arene building element with methylene, and has the characteristics of special structure, easy synthesis and derivatization, electron-rich cavity and the like, so that great attention is paid to the macrocyclic arene. In recent years, in addition to classical macrocyclic arenes such as column arenes and calixarene, various other novel structures of macrocyclic arenes have been reported successively, such as prismatic arenes, tower arenes, geminiarenes, crown arenes, helical tower arenes, spiroarenes, and the like. Therefore, the development of novel macrocyclic arenes with structural and functional features has become the leading edge and hotspot for supramolecular chemistry research.
Biphenylarenes are an emerging class of macrocyclic aromatic compounds, whose modular synthetic strategies enable the introduction of different functional motifs into the macrocyclic skeleton, enabling customizable synthesis of functional macrocycles in size, shape and skeleton functional motifs (acc. Chem. Res. 2022, 55, 916). However, the synthesized biphenyl arene functional macrocyclic molecules are almost flexible planar structures, and have no effective rigid three-dimensional cavity structure, so that the main and guest identification properties are lost, and the application of the biphenyl arene functional macrocyclic molecules is limited. Therefore, it is very interesting to introduce functional motifs with rigid steric structures into the macrocyclic skeleton to achieve the synthesis of macrocycles with unique cavity structures and molecular recognition capabilities.
Disclosure of Invention
The invention aims to provide a Tr foster's Base skeleton macrocyclic compound, a preparation method and application thereof, wherein the macrocyclic compound has chiral, rigid and electron-rich cavities and presents a molecular box-shaped topological structure. The method can efficiently identify the 1,3, 5-Benzene Tricarbonitrile (BTCN) through intermolecular charge transfer, and assemble to form a stable host-guest 1:1 compound, wherein the compound shows organic room temperature phosphorescence property and has potential application in information encryption and security anti-counterfeiting.
The invention aims at realizing the following technical scheme:
The invention provides a Tr foster's Base skeleton macrocyclic compound, which contains a reverse V-shaped Tr, and presents a molecular box-shaped three-dimensional topological structure, wherein the macrocyclic compound structure is shown as a formula I or a formula II, and the structure shown as the formula I or the formula II contains meso and raceme:
furthermore, the meso and racemic compounds of the structure shown in the formula I can efficiently identify BTCN molecules with electron deficiency, and the complexation constant between main and guest bodies in an organic phase is up to 10 4 M-1.
The invention also provides a 1:1 host-guest complex crystal, which is formed into a stable 1:1 host-guest complex crystal by self-assembly of meso and racemic bodies of the structure shown in the formula I and BTCN under the solid state through intermolecular charge transfer, wherein the unit cell parameters of the crystal structure are as follows ：a = 47.0026(6), b = 17.48110(10), c = 37.8949(3), α = 90o, β = 115.0950o(10), γ = 90o; a = 18.4552(2), b = 18.86825(17), c = 22.7686(2), α = 90o, β = 108.5830(12), γ = 90o.
The invention also provides a preparation method of the Tr ger's Base skeleton macrocyclic compound, which comprises the following steps:
(1) The compound 1 and 2, 4-or 2, 5-dimethoxy phenylboronic acid are respectively synthesized into a monomer compound 2 or a monomer compound 3 through Suzuki-Miyaura coupling reaction, and the specific reaction scheme is shown in a formula III;
Formula III
(2) The monomer compound 2 or 3 and paraformaldehyde undergo Friedel-crafts alkylation reaction under the catalysis of Lewis acid, a macrocyclic compound shown as a formula I or a formula II can be prepared by a one-pot method, meso and raceme shown as the formula I or the formula II are obtained by separation and purification through a column chromatography, and a specific reaction flow is shown as a formula IV;
Formula IV.
Further, the Lewis acid catalyst is any one of trifluoroacetic acid, p-toluenesulfonic acid, boron trifluoride diethyl ether, trifluoromethanesulfonic acid and ferric trichloride.
Further, the Lewis acid catalyst is trifluoroacetic acid.
Further, in the step (1), the specific steps of the Suzuki-Miyaura coupling reaction are as follows: and (2) mixing the compound 1 with 2, 4-or 2, 5-dialkoxyphenylboronic acid according to the molar quantity of 1:2-3, dissolving in a mixed solution of dioxane and water (v: v=5:1), adding 4 equivalents of potassium carbonate and 10% of catalytic quantity of 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride, heating, stirring and refluxing for 12 hours under the protection of argon, cooling the reaction solution to room temperature after the reaction is finished, extracting with dichloromethane and water for three times, mixing an organic phase silica gel sample, and obtaining the monomer compound 2 and the monomer compound 3 through column chromatography.
Further, in the step (2), the friedel-crafts alkylation reaction specifically includes: the monomer compound 2 or 3 and paraformaldehyde are mixed and dissolved in methylene dichloride according to the mol ratio of 1:2.5, then a catalytic amount of Lewis acid is added, after 45 min of reaction, the reaction is quenched by saturated sodium bicarbonate aqueous solution, the organic phase is stirred by silica gel, and the meso-and racemic bodies of the dimer macrocyclic compounds shown in the formulas I and II are obtained through separation and purification by column chromatography.
The invention also provides application of the Tr ger's Base skeleton macrocyclic compound or the 1:1 host-guest complex crystal in organic room-temperature phosphorescence, information encryption and safe anti-counterfeiting.
Wherein, meso and raceme of the macrocyclic compound in the formula I can efficiently recognize BTCN molecules of complex electron deficiency in an organic phase, and the complex constants are (3.9+/-0.4) multiplied by 10 3 M-1、(8.4 ± 0.8) × 104 M-1 respectively. The assembly driving force between molecules is charge transfer. And the 1:1 composite crystal formed by assembling the host and the guest in a solid state shows the phosphorescence performance at the organic room temperature and has potential application in the aspects of information encryption and security and anti-counterfeiting.
The invention has the beneficial effects that:
(1) According to the invention, the Tr foster's Base skeleton element with chiral, rigid and open inverted V-type three-dimensional configuration is introduced into the diphenyl arene series macrocycle, so that the diphenyl arene functional macrocycle has an effective rigid cavity structure and molecular recognition capability. The preparation method is simple and efficient, and has high yield.
(2) The Tr foster's Base macrocyclic molecule provided by the invention can realize extremely strong complexation of BTCN molecules with neutral electron deficiency in an organic solvent due to the matching property of the cavity size and the electrical property, and the complexation constant is as high as 10 4 M-1, which is difficult to realize by complexation of BTCN in an organic phase of the traditional macrocyclic molecule.
(3) The host-guest complex formed by complexing the Tr back-er's Base macrocycle and BTCN has organic room-temperature phosphorescence property, and the host-guest crystal material formed by the macrocycle through charge transfer is novel in realizing the organic room-temperature phosphorescence property.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of monomer 2 in example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of monomer 3 in example 1;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the meso form of the macrocyclic compound of example 2;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the racemate of the macrocyclic compound of formula I in example 2;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the meso form of the macrocyclic compound of formula II in example 2;
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of the racemate of the macrocyclic compound of formula II in example 2;
FIG. 7 is a 1:1 nuclear magnetic resonance spectrum of the meso form and BTCN of the macrocyclic compound of formula II in example 3;
FIG. 8 is a 1:1 nuclear magnetic resonance spectrum of racemate and BTCN of macrocyclic compound of formula II in example 3;
FIG. 9 is a plot of a nuclear magnetic titration fit of the meso form of the macrocyclic compound of formula I in example 3 to BTCN;
FIG. 10 is a plot of the fit of the racemate of the macrocyclic compound of formula I to the nuclear magnetic titration of BTCN in example 3;
FIG. 11 is a schematic illustration of the meso and BTCN host single crystal structure of the macrocyclic compound of formula I in example 4;
FIG. 12 is a diagram showing the structure of the racemate of the macrocyclic compound of formula I and the host guest single crystal of BTCN in example 4;
FIG. 13 is a graph showing phosphorescence spectrum of a complex of a meso form of the macrocyclic compound of formula I in example 5 with BTCN;
FIG. 14 is a phosphorescence spectrum of a complex of racemate of the macrocyclic compound of formula I and BTCN;
FIG. 15 is a graph of phosphorescent lifetime of a meso form of the macrocyclic compound of formula I in example 5 with BTCN complexes;
FIG. 16 is a graph of phosphorescent lifetime of a racemate of the macrocyclic compound of formula I in example 5 with BTCN complexes.
Detailed Description
The invention is described below by means of specific embodiments. The technical means used in the present invention are methods well known to those skilled in the art unless specifically stated. Further, the embodiments should be construed as illustrative, and not limiting the scope of the invention, which is defined solely by the claims. Various changes or modifications to the materials ingredients and amounts used in these embodiments will be apparent to those skilled in the art without departing from the spirit and scope of the invention.
The method of the present invention for the use of compound 1 is described in the publication of Satyajit Saha et al, new J.chem., volume 44, 2020, pages 12331-12342. The reagents used for the preparation of the catalyst, such as 1,3, 5-triphenyl nitrile, 2, 4-dimethoxy phenylboronic acid, 2, 5-dimethoxy phenylboronic acid and the like, are all commercial raw materials.
EXAMPLE 1 preparation of monomer Compounds
Compound 1 was mixed with 2, 4-or 2, 5-dialkoxyphenylboronic acid (5.0 g, 13.2 mmol) and dissolved in a mixed solution of 100 mL dioxane (100 mL) and water (20 mL), then potassium carbonate (7.3 g, 52.6 mol) and 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride (0.48 g, 0.66 mmol) were added, and after the reaction was completed, the reaction solution was heated and refluxed for 12 hours under argon protection, and was cooled to room temperature, extracted three times with dichloromethane and water, and the organic phase was stirred with silica gel, and then the monomer compound 2 (6.3 g, 97% yield) and compound 3 (6.1 g) were obtained by column chromatography, 94% yield. The nuclear magnetic hydrogen spectrograms of the compounds 2 and 3 are shown in fig. 1 and 2, and the specific reaction scheme is shown in a formula III.
Formula III
EXAMPLE 2 preparation of macrocyclic Compounds
Monomer compound 2 or 3 (1.0 g, 2.0 mmol) was dissolved in 100mL methylene chloride, paraformaldehyde (0.15 g, 2.5 eq) was added to the reaction system, trifluoroacetic acid (2 mL, 26.9 mmol) was added to the reaction system after stirring at normal temperature for 45min, the reaction was quenched with saturated aqueous sodium bicarbonate solution, washed with saturated sodium chloride solution, dried organic phase with anhydrous sodium sulfate, stirred with silica gel, and purified by column chromatography to obtain the dimeric macrocyclic compound of formula I and formula II, and both of them were isolated to obtain their meso-and racemic structures (formula I: 0.89 g, yield 87%; formula II: 0.86 g, yield 84%). The meso form and the racemate nuclear magnetic hydrogen spectrogram of the compound shown in the formula I are shown in fig. 3 and 4, the meso form and the racemate nuclear magnetic hydrogen spectrogram of the compound shown in the formula II are shown in fig. 5 and 6, and the specific reaction flow is shown in the formula IV.
IV (IV)
Example 3 subject and guest identification study
1 H NMR investigated the main guest complexation of the meso and racemic forms of the compounds of formula i with BTCN in solution. As shown in fig. 7 and 8, when equimolar amount of macrocyclic compound is added to BTCN of deuterated chloroform solution, the proton H a signal peak on the guest BTCN is not seen, indicating BTCN interpenetrates in the cavities of the macrocyclic molecule to form a 1:1 host-guest interpenetrating structure, so that the guest proton signal is shielded. At the same time, protons H 1、H3、H4 and H 5 on the body are subject to a de-screening effect, and chemical shifts are respectively significantly shifted to low fields.
In order to quantitatively evaluate the bonding strength between host and guest, the complex constants (K a) of the meso and racemic forms of the compound of formula i, respectively, with BTCN in a CDCl 3:CCl4 =1:1 mixed solvent were measured by nuclear magnetic titration. In this system, the complexation of the host and guest is fast-swapped with respect to the 1 H NMR time scale. The concentration of the fixed host is 0.5 mM, the concentration of the object is gradually increased, according to the changing object concentration and the chemical shift change value of protons on the aromatic ring of the host, the K a value between the host and the object is calculated to be (3.9+/-0.4) multiplied by 10 3 M-1、(8.4 ± 0.8) × 104 M-1 respectively by a nonlinear fitting method according to a 1:1 fitting formula, and the nonlinear fitting curves are shown in fig. 9 and 10.
EXAMPLE 4 preparation of host-guest Complex and Crystal Structure
10 Mg of the meso or racemic macrocyclic compound of formula I and 3mg BTCN are weighed, added to a 2mL chloroform solution, dissolved well and filtered through a 0.22 μm organic filter. Transferring the filtered solution into a 5mL glass bottle, placing the solution into a 20 mL large glass bottle containing isopropyl ether, covering a bottle cap, completely sealing, and diffusing for 3 days at normal temperature to obtain the host-guest complex crystal. Single crystal X-ray diffraction analysis showed BTCN to be able to stably complex within the macrocyclic cavity by intermolecular C-H … pi and charge transfer, forming a 1:1 host-guest complex with a crystal structure shown in fig. 11 and 12.
EXAMPLE 5 phosphorescent Properties of host-guest complexes
The host-guest complex of formula I was subjected to phosphorescence test, and the organic room temperature phosphorescent material had significant phosphorescence emission characteristics. The host-guest complex of meso and BTCN has a main peak of phosphorescence emission at 515: 515 nm and a phosphorescence lifetime of 9.80 μs, as shown in figures 13 and 15; the host-guest co-crystal of racemate and BTCN had a phosphorescence emission main peak at 496 nm and a phosphorescence lifetime of 9.56 ms, as shown in fig. 14 and 16.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (5)
1. The method comprises the following steps ofA Base skeleton macrocyclic compound characterized in that the/>The Base skeleton macrocyclic compound contains a 'Λ' -type/>The Base chiral functional framework presents a molecular box-shaped three-dimensional topological structure, and the macrocyclic compound is shown as a formula I, wherein the structure shown as the formula I contains meso and raceme:
2. a1:1 host-guest complex crystal is characterized in that 10mg of meso or racemic macrocyclic compound of formula I and 3mg BTCN are weighed, added into 2mL of chloroform solution, fully dissolved, filtered by a 0.22 mu m organic filter membrane, transferred into a 5mL glass bottle, placed into a20 mL large glass bottle containing isopropyl ether, covered with a bottle cap, fully closed, diffused for 3 days at normal temperature, and self-assembled by intermolecular charge transfer to form a stable 1:1 host-guest complex crystal, and the unit cell parameters of the crystal structure are as follows ：a＝47.0026(6),b＝17.48110(10),c＝37.8949(3),α＝90°,β＝115.0950°(10),γ＝90°;a＝18.4552(2),b＝18.86825(17),c＝22.7686(2),α＝90°,β＝108.5830(12),γ＝90°.
3. The method comprises the following steps ofThe preparation method of the Base skeleton macrocyclic compound is characterized by comprising the following steps:
(1) The compound 1 and 2, 4-dimethoxy phenylboronic acid are subjected to a Suzuki-Miyaura coupling reaction to synthesize a monomer compound 2, and the specific reaction scheme is shown in a formula III;
(2) The monomer compound 2 and paraformaldehyde undergo Friedel-crafts alkylation reaction under the catalysis of Lewis acid, a macrocyclic compound shown as a formula I can be prepared by a one-pot method, meso and raceme shown as the formula I are obtained by separation and purification through a column chromatography, and a specific reaction flow is shown as a formula IV;
The Lewis acid is any one of trifluoroacetic acid, p-toluenesulfonic acid, boron trifluoride diethyl etherate, trifluoromethanesulfonic acid and ferric trichloride;
in the step (1), the specific steps of the Suzuki-Miyaura coupling reaction are as follows: mixing and dissolving a compound 1 and 2, 4-dialkoxyphenylboronic acid in a molar amount of 1:2-3 in a mixed solution of dioxane and water (v: v=5:1), adding 4 equivalents of potassium carbonate and 10% of catalytic amount of 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride, heating, stirring and refluxing for 12 hours under the protection of argon, cooling a reaction solution to room temperature after the reaction is finished, extracting with dichloromethane and water for three times, mixing an organic phase silica gel sample, and obtaining a monomer compound 2 through column chromatography;
In the step (2), the specific steps of the friedel-crafts alkylation reaction are as follows: mixing and dissolving the monomer compound 2 and paraformaldehyde in a molar ratio of 1:2.5 in dichloromethane, adding a catalytic amount of Lewis acid, quenching the reaction with saturated sodium bicarbonate aqueous solution after the reaction is carried out for 45min, mixing an organic phase with silica gel, and separating and purifying by a column chromatography method to obtain meso and racemate of the dimer macrocyclic compound shown in the formula I.
4. A method according to claim 3The preparation method of the Base skeleton macrocyclic compound is characterized in that the Lewis acid is trifluoroacetic acid.
5. The method as claimed in claim 1The application of the Base skeleton macrocyclic compound or the 1:1 host-guest complex crystal in organic room temperature phosphorescence, information encryption and security anti-counterfeiting according to claim 2.
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| Amorphous Host Materials Based on Tröger’s Base Scaffold for Application in Phosphorescent Organic Light-Emitting Diodes;Ishita Neogi，等;ACS Appl. Mater. Interfaces;20150113;第7卷;全文 * |
| Chiral selection of Tröger’s base-based macrocycles with different ethylene glycol chains length in crystallization;Haohui Feng，等;Chinese Chemical Letters;20221205;第34卷;全文 * |
| New boomerang-shaped host materials for phosphorescent organic light-emitting diodes;Ishita Neogi，等;Synthetic Metals;20220915;第291卷;全文 * |
| Rong Fu,等.A Chiral Emissive Conjugated Corral for High-Affinity and Highly Enantioselective Recognition in Water.Angew. Chem. Int. Ed..2023,第62卷全文. * |
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