CN113087640A - Chiral ONO tridentate Schiff base carboxylic acid ligand and preparation method and application thereof - Google Patents
Chiral ONO tridentate Schiff base carboxylic acid ligand and preparation method and application thereof Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 70
- 239000002262 Schiff base Substances 0.000 title claims abstract description 43
- -1 Schiff base carboxylic acid Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 238000006243 chemical reaction Methods 0.000 claims description 25
- 229910017052 cobalt Inorganic materials 0.000 claims description 24
- 239000010941 cobalt Substances 0.000 claims description 24
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011449 brick Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- LOPKSXMQWBYUOI-BDAKNGLRSA-N (1s,2r)-1-amino-2,3-dihydro-1h-inden-2-ol Chemical compound C1=CC=C2[C@H](N)[C@H](O)CC2=C1 LOPKSXMQWBYUOI-BDAKNGLRSA-N 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000004753 Schiff bases Chemical class 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 239000011365 complex material Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a chiral ONO tridentate Schiff base carboxylic acid ligand, which relates to the technical field of coordination compounds and has the following structural formula:
the invention also provides a preparation method of the ligand and a complex based on the ligand. The invention has the beneficial effects that: the chiral ONO tridentate Schiff base carboxylic acid ligand prepared by the invention can be prepared by simply reacting cheap raw materials and abundant chiral sources, is favorable for reducing the preparation cost and the synthesis difficulty of the chiral ligand, and contains a unique ONO chelating coordination mode, thereby being favorable for preparing Schiff base chiral complexes with abundant structures.
Description
Technical Field
The invention relates to the technical field of coordination compounds, in particular to a chiral ONO tridentate Schiff base carboxylic acid ligand and a preparation method and application thereof.
Background
The coordination compound is also called as a complex or a complex and the like, is a compound which is formed by combining a bridging ligand containing a specific electron donor and a central metal ion through a coordination bond and has a specific structure and functions, and has the advantages of easy modification of an organic ligand and high stability of an inorganic unit, and has a definite structure, rich topology, various pore channels and adjustable functions, so that the coordination compound is widely concerned in the fields of gas storage, fluorescence sensing, catalytic separation, environmental protection energy, drug slow release and the like.
In recent years, complex materials with chiral structures can provide unique chiral environments, so that the complex materials have great application prospects in asymmetric synthesis and chiral separation, but the chiral complex materials have the factors of difficult synthesis, high cost and the like, and the development of the complex materials is severely restricted. Therefore, researchers have focused more on designing chiral ligands with specific connection modes and rigid conjugated systems to control the structure and chiral function of coordination materials.
The Schiff base compound has N in view of symmetry2O2The ligand pocket of (a) to become a preferred ligand for constructing chiral complex materials, and related complex materials have been reported in documents, for example, patent application with publication No. CN104327125A discloses a hetero metal complex of carboxylic acid Schiff base iron zinc and a preparation method thereof, and the complex has chelation in an internal cavity [ N ] with chelate2O2]And synthesizing the hetero-metal complex by the Schiff base ligand of the coordination site. But is chiral inThe source is expensive, the coordination mode is relatively simple, and the chiral complex material with richer structure is not easy to obtain.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an ONO tridentate chiral Schiff base carboxylic acid ligand with an asymmetric structure, a preparation method thereof and a cobalt-based chiral complex constructed based on the ligand, wherein the cobalt-based chiral complex is a chiral supramolecular crystal with a unique two-dimensional network structure.
The invention solves the technical problems through the following technical means:
chiral ONO tridentate Schiff base carboxylic acid ligand L-H3The structural formula is as follows:
has the advantages that: the chiral ligand has cheap synthetic raw materials and simple preparation method, and is beneficial to large-scale preparation; in addition, the framework of the chiral ligand of the invention simultaneously has ONO tridentate chelating sites and carboxyl groups, and the chiral ligand is easy to be chelated and coordinated with metal ions to generate chiral complex materials with different structures.
The invention also provides a chiral ONO tridentate Schiff base carboxylic acid ligand L-H3The preparation method comprises the following steps:
1) dissolving 4-methyl hydroxybenzoate and 1-adamantanol in dichloromethane, adding concentrated sulfuric acid, stirring at room temperature, reacting for 4-8 hours, adding a low-concentration sodium hydroxide solution to adjust the pH value of the mixed reaction solution to be neutral, extracting an organic phase by using ethyl acetate, and drying and concentrating to obtain a crude product of 3-adamantane-4-methyl hydroxybenzoate;
2) dissolving 3-adamantane-4-hydroxybenzoic acid methyl ester, paraformaldehyde, triethylamine and anhydrous magnesium chloride in acetonitrile to prepare a mixed reaction solution, reacting at 80 ℃ for 12-16 hours, adjusting the pH value to be neutral by using dilute hydrochloric acid, extracting an organic phase by using ethyl acetate, drying and concentrating, and then separating and purifying by using a chromatographic column to obtain an intermediate 3-adamantane-5-aldehyde-4-hydroxybenzoic acid methyl ester;
3) dissolving 3-adamantane-5-aldehyde-4-hydroxybenzoic acid methyl ester and lithium hydroxide in a mixed solvent of methanol, tetrahydrofuran and water, reacting the obtained reaction mixed solution at 60 ℃ for 5-8 hours, adjusting the pH of the reaction mixed solution to 2 by using dilute hydrochloric acid, washing and drying a large amount of separated white solid to obtain a ligand precursor 3-adamantane-5-aldehyde-4-hydroxybenzoic acid, and putting the ligand precursor 3-adamantane-5-aldehyde-4-hydroxybenzoic acid into the next condensation reaction;
4) dissolving 3-adamantane-5-aldehyde-4-hydroxybenzoic acid and (1S,2R) -1-amino-2, 3-dihydro-1H-indene-2-alcohol in methanol, performing reflux reaction at 70 ℃ for 18-24 hours, directly filtering to obtain yellow mud, and purifying to obtain chiral ONO tridentate Schiff base carboxylic acid ligand L-H3。
Has the advantages that: the chiral ONO tridentate Schiff base carboxylic acid ligand prepared by the invention is obtained by simple organic reaction of cheap and easily-obtained raw materials and a chiral source, has low preparation cost, simple synthesis method and strong operability, and is beneficial to large-scale preparation of the chiral ligand.
Preferably, the ratio of the amounts of substances of the methyl 4-hydroxybenzoate and the 1-adamantanol in the step 1) is 1:1, and the sulfuric acid is a catalytic equivalent.
Preferably, the mass ratio of the methyl 3-adamantane-4-hydroxybenzoate, the paraformaldehyde, the triethylamine and the anhydrous magnesium chloride in the step 2) is 1:2:6: 10.
Preferably, the mass ratio of the 3-adamantane-5-aldehyde-4-hydroxybenzoic acid methyl ester to the lithium hydroxide in the step 3) is 1:10, and the volume ratio of the methanol to the tetrahydrofuran to the water is 4: 4: 1.
preferably, the ratio of the amounts of substances of the 3-adamantane-5-aldehyde-4-hydroxybenzoic acid and the (1S,2R) -1-amino-2, 3-dihydro-1H-inden-2-ol in the step 4) is 1: 1.
The invention also provides a cobalt-based chiral complex based on the ONO tridentate Schiff base, the complex takes cobalt as a metal center, the ONO tridentate Schiff base as a chiral ligand, 4, 4' -bipyridine (bpy) as an auxiliary ligand, and the molecular formula of the complex is { [ Co (L-H) (bpy) · MeOH]·MeOH}nThe structural formula of the complex is shown in the specificationThe following:
Has the advantages that: the chiral Schiff base carboxylic acid ligand containing an ONO tridentate chelating site and the cobalt salt are utilized to carry out self-assembly coordination, and the asymmetric structure of the Schiff base ligand enables the structure of the complex to be more diverse; in addition, carboxyl at the tail end of the cobalt-based chiral complex which does not participate in coordination can be used as a hydrogen bond site to construct a two-dimensional net-shaped chiral supramolecular structure.
Preferably, the unit cell parameters of the cobalt-based chiral complex single crystal are as follows:
α＝69.132(2)°,β＝79.9662(2)°,γ＝77.104(2)°，
the invention also provides a preparation method of the cobalt-based chiral complex based on the ONO tridentate Schiff base, which comprises the following steps:
1) preparing a reaction mixed solution: adding a chiral ONO tridentate Schiff base carboxylic acid ligand, bpy and a cobalt salt into a mixed solvent, and fully stirring and dissolving at normal temperature to obtain a reaction mixed solution;
2) and (3) crystallization reaction: and (2) placing the reaction mixed solution prepared in the step 1) in a constant-temperature air-blast drying oven at the temperature of 60-80 ℃ for reacting for 48-72 hours to obtain brick red blocky crystals, and then filtering and washing to obtain the cobalt-based chiral complex.
Has the advantages that: the synthetic method is simple, convenient and feasible, and has high operability.
Preferably, the molar ratio of the chiral ONO tridentate Schiff base carboxylic acid ligand, bpy and cobalt salt in the step 1) is 1:1: 2.
preferably, the cobalt salt in step 1) is CoCl2。
Preferably, the mixed solvent in the step 1) is prepared by mixing N, N' -dimethylformamide, methanol (MeOH) and water, and the volume ratio of the dimethylformamide to the methanol to the water is 1:6: 1.
The invention has the advantages that:
the chiral ligand has cheap synthetic raw materials and simple preparation method, and is beneficial to large-scale preparation; in addition, the framework of the chiral ligand of the invention simultaneously has ONO tridentate chelating sites and carboxyl groups, and the chiral ligand is easy to be chelated and coordinated with metal ions to generate chiral complex materials with different structures.
The chiral ONO tridentate Schiff base carboxylic acid ligand prepared by the invention is obtained by simple organic reaction of cheap and easily-obtained raw materials and a chiral source, has low preparation cost, simple synthesis method and strong operability, and is beneficial to large-scale preparation of the chiral ligand.
The chiral Schiff base carboxylic acid ligand containing an ONO tridentate chelating site and the cobalt salt are utilized to carry out self-assembly coordination, and the asymmetric structure of the Schiff base ligand enables the structure of the complex to be more diverse; in addition, carboxyl at the tail end of the cobalt-based chiral complex which does not participate in coordination can be used as a hydrogen bond site to construct a two-dimensional net-shaped chiral supramolecular structure.
The synthetic method is simple, convenient and feasible, and has high operability.
Drawings
FIG. 1 shows chiral ONO tridentate Schiff base carboxylic acid ligands L-H in an embodiment of the invention3Schematic diagram of the synthetic route of (1).
FIG. 2 chiral ONO tridentate Schiff base carboxylic acid ligands L-H in an embodiment of the invention3Nuclear magnetic resonance hydrogen spectrum of (a).
FIG. 3 is a crystal structure diagram of a cobalt-based chiral complex in example 1 of the present invention.
FIG. 4 is a one-dimensional chain structure diagram of a cobalt-based chiral complex in example 1 of the present invention.
FIG. 5 is a diagram of a two-dimensional network supramolecular structure formed by a cobalt-based chiral complex through hydrogen bonding (hydrogen bonding is shown by a dotted line) in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
Weighing chiral ONO tridentate Schiff base carboxylic acid ligand L-H according to the mass ratio of 1:1:23Auxiliary ligand bpy and metal salt CoCl2Dissolving the cobalt-based chiral complex in a mixed solution of 1mL of distilled water, 1mL of N, N' -dimethylformamide and 6mL of methanol, stirring the mixed solution at room temperature for about 5 minutes to fully mix the mixture, then placing the mixed solution in a stainless steel reaction kettle with a 20mL polytetrafluoroethylene lining, sealing the stainless steel reaction kettle, reacting the mixture at 60 ℃ for 72 hours, cooling the mixture to room temperature, filtering, washing and drying the mixture to obtain brick red blocky crystals of the cobalt-based chiral complex, wherein the yield is about 45 percent (based on ligand L-H)3)。
Wherein, ONO tridentate chiral Schiff base carboxylic acid ligand L-H3The preparation method is as follows, and the synthetic route is shown in figure 1:
1) dissolving methyl 4-hydroxybenzoate and 1-adamantanol with the mass ratio of 1:1 in dichloromethane, adding catalytic amount of concentrated sulfuric acid, stirring at room temperature for 4 hours, and adding 1 mol.L-1The pH value of the reaction mixture is adjusted to be neutral by the sodium hydroxide solution, the organic phase is extracted by ethyl acetate, and then the 3-adamantane-4-hydroxybenzene is obtained by drying and concentrationThe purity of the methyl formate crude product can be directly used for the next reaction;
2) putting a reaction mixture of methyl 3-adamantane-4-hydroxybenzoate, paraformaldehyde, triethylamine and anhydrous magnesium chloride with the mass ratio of 1:2:6:10 into a 500mL reaction bottle, adding a proper amount of anhydrous treated acetonitrile solvent, stirring and reacting at 80 ℃ for 12 hours, cooling to room temperature, and reacting with 1 mol.L-1Regulating the pH value of the reaction mixed solution to be neutral by hydrochloric acid, extracting an organic phase by using ethyl acetate, drying, concentrating, and then separating and purifying by a chromatographic column to obtain an intermediate 3-adamantane-5-aldehyde-4-hydroxybenzoic acid methyl ester;
3) 3-adamantane-5-aldehyde-4-hydroxybenzoic acid methyl ester and lithium hydroxide are mixed according to the mass ratio of 1:10, dissolving the mixture into a mixed solvent of methanol, tetrahydrofuran and water (the volume ratio is 4: 4: 1), stirring the mixture for reaction for 5 hours at the temperature of 60 ℃, adjusting the pH of the reaction mixed solution to be 2 by using dilute hydrochloric acid, so that a large amount of white solid is separated out, filtering, washing and drying the solid to obtain a ligand precursor 3-adamantane-5-aldehyde-4-hydroxybenzoic acid, and directly putting the ligand precursor into the next condensation reaction without purification;
4) 3-adamantane-5-aldehyde-4-hydroxybenzoic acid and (1S,2R) -1-amino-2, 3-dihydro-1H-inden-2-ol (the ratio of the amounts of the substances is 1: 1) dissolving in appropriate amount of anhydrous methanol, reflux reacting at 70 deg.C for 18 hr to obtain yellow mud, filtering, and washing with hot methanol for 2 times to obtain pure ONO tridentate chiral Schiff base carboxylic acid ligand L-H3。
FIG. 2 shows ONO tridentate chiral Schiff base carboxylic acid ligands L-H3The nuclear magnetic resonance hydrogen spectrogram shows that the ligand is successfully synthesized.
Example 2
Weighing the chiral ONO tridentate Schiff base carboxylic acid ligand L-H in the example 1 according to the mass ratio of 1:1:23Auxiliary ligand bpy and metal salt CoCl2Dissolving in a mixed solution of 1mL of distilled water, 1mL of N, N' -dimethylformamide and 6mL of methanol, stirring at room temperature for about 5 minutes to mix thoroughly, placing the mixed solution in a 20mL polytetrafluoroethylene liner, sealing in a stainless steel reaction kettle, and keeping the temperature at 80 DEG CAnd reacting for 48 hours, cooling to room temperature, filtering, washing and drying to obtain brick red blocky crystals of the cobalt-based chiral complex.
Experimental data and characterization:
the crystal structure of the cobalt-based chiral complex based on ONO tridentate schiff base obtained in example 1 was determined.
The determination method comprises the following steps: selecting a single crystal sample with proper size, placing the single crystal sample in a Bruker CCDII diffractometer and adopting Mo-Kα 
Collecting diffraction data for incident light source, restoring the diffraction data by using the program of the instrument, and performing structure analysis and refinement by using the SHELXS-2014 program, wherein the diffraction data are collected by a full-matrix least square method (full-matrix least-squares detailed on F)2) All non-hydrogen atoms were defined and anisotropic refinement of the atoms was accomplished. In addition ligands L-H3And the hydrogen atom in bpy is completed by theoretical hydrogenation
And (3) measuring results: the crystal cell parameter of the cobalt-based chiral complex single crystal is
α＝69.132(2)°,β＝79.9662(2)°,γ＝77.104(2)°，
The complex was analytically found to crystallize in the chiral P1 space group, which contains asymmetric units and its molecular formula { [ Co (L-H) (bpy) · MeOH { []·MeOH}nBeing coherent, i.e. containing 1 Co2+Ions, 1 deprotonated L-H ligand molecule, 1 bpy molecule, 1 coordinated methanol molecule and 1 free methanol molecule, as shown in FIG. 3. Center of chiral complexCo2+Adopting a distorted octahedral coordination mode, wherein four coordination sites of an equatorial plane of the octahedral coordination; ligand L-H3And Co2 +The metal ligand Co (L-H) formed by chelating the ions is further assembled into a chain structure under the coordination of bpy molecules, as shown in figure 4; since the terminal carboxyl group of the metal ligand does not participate in coordination, it can be used as a hydrogen bonding group to further assemble the adjacent one-dimensional chain structure into a two-dimensional network-like chiral supramolecular structure as shown in FIG. 5, wherein the hydrogen bonding action
Indicated by dashed lines.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A chiral ONO tridentate Schiff base carboxylic acid ligand is characterized in that: the structural formula is as follows:
2. process for the preparation of chiral ONO tridentate schiff base carboxylic acid ligands according to claim 1, characterized in that: the method comprises the following steps:
1) dissolving 4-methyl hydroxybenzoate and 1-adamantanol in dichloromethane, adding concentrated sulfuric acid, stirring at room temperature, reacting for 4-8 hours, adding a low-concentration sodium hydroxide solution to adjust the pH value of the mixed reaction solution to be neutral, extracting an organic phase by using ethyl acetate, and drying and concentrating to obtain a crude product of 3-adamantane-4-methyl hydroxybenzoate;
2) dissolving 3-adamantane-4-hydroxybenzoic acid methyl ester, paraformaldehyde, triethylamine and anhydrous magnesium chloride in acetonitrile to prepare a mixed reaction solution, reacting at 80 ℃ for 12-16 hours, adjusting the pH value to be neutral by using dilute hydrochloric acid, extracting an organic phase by using ethyl acetate, drying and concentrating, and then separating and purifying by using a chromatographic column to obtain an intermediate 3-adamantane-5-aldehyde-4-hydroxybenzoic acid methyl ester;
3) dissolving 3-adamantane-5-aldehyde-4-hydroxybenzoic acid methyl ester and lithium hydroxide in a mixed solution of methanol, tetrahydrofuran and water, reacting for 5-8 hours at 60 ℃, adjusting the pH of the reaction mixed solution to 2 by using dilute hydrochloric acid, then washing and drying a large amount of precipitated white solid to obtain a ligand precursor 3-adamantane-5-aldehyde-4-hydroxybenzoic acid, and putting the ligand precursor into the next step of condensation reaction;
4) dissolving 3-adamantane-5-aldehyde-4-hydroxybenzoic acid and (1S,2R) -1-amino-2, 3-dihydro-1H-indene-2-alcohol in methanol, carrying out reflux reaction at 70 ℃ for 18-24 hours, directly filtering to obtain yellow mud, and purifying to obtain the chiral ONO tridentate Schiff base carboxylic acid ligand.
3. The method of claim 2, wherein the chiral ONO tridentate schiff base carboxylic acid ligand is prepared by: the mass ratio of the methyl 4-hydroxybenzoate to the 1-adamantanol in the step 1) is 1:1, and the sulfuric acid is catalytic equivalent.
4. The method of claim 2, wherein the chiral ONO tridentate schiff base carboxylic acid ligand is prepared by: the mass ratio of the 3-adamantane-4-hydroxybenzoic acid methyl ester, the paraformaldehyde, the triethylamine and the anhydrous magnesium chloride in the step 2) is 1:2:6: 10.
5. The method of claim 2, wherein the chiral ONO tridentate schiff base carboxylic acid ligand is prepared by: in the step 3), the mass-to-mass ratio of the 3-adamantane-5-aldehyde-4-hydroxybenzoic acid methyl ester to the lithium hydroxide is 1:10, and the volume ratio of the methanol to the tetrahydrofuran to the water is 4: 4: 1.
6. the method of claim 2, wherein the chiral ONO tridentate schiff base carboxylic acid ligand is prepared by: the mass ratio of the 3-adamantane-5-aldehyde-4-hydroxybenzoic acid to the (1S,2R) -1-amino-2, 3-dihydro-1H-indene-2-ol in the step 4) is 1: 1.
7. A cobalt-based chiral complex based on the chiral ONO tridentate schiff base carboxylic acid ligand of claim 1, characterized in that: the complex takes cobalt as a metal center, ONO tridentate Schiff base carboxylic acid as a chiral ligand and 4, 4' -bipyridine (bpy) as an auxiliary ligand, and the molecular formula of the complex is { [ Co (L-H) (bpy) · MeOH]·MeOH}nThe structural formula of the complex is as follows:
8. The cobalt-based chiral complex of claim 7, wherein: the unit cell parameters of the cobalt-based chiral complex single crystal are as follows:
α＝69.132(2)°,β＝79.9662(2)°,γ＝77.104(2)°，
9. a process for preparing a cobalt-based chiral complex of claim 7, wherein: the method comprises the following steps:
1) preparing a reaction mixed solution: adding a chiral ONO tridentate Schiff base carboxylic acid ligand, bpy and a cobalt salt into a mixed solvent, and fully stirring and dissolving at normal temperature to obtain a reaction mixed solution;
2) and (3) crystallization reaction: and (2) placing the reaction mixed solution prepared in the step 1) in a constant-temperature air-blast drying oven at the temperature of 60-80 ℃ for reacting for 48-72 hours to obtain brick red blocky crystals, and then filtering and washing to obtain the cobalt-based chiral complex.
10. The method for preparing a cobalt-based chiral complex according to claim 9, wherein: the molar ratio of the chiral ONO tridentate Schiff base carboxylic acid ligand to the bpy to the cobalt salt in the step 1) is 1:1: 2.
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