CN111154115A - Preparation method and application of binuclear Ir (III) metal-organic supermolecular cage-like compound - Google Patents
Preparation method and application of binuclear Ir (III) metal-organic supermolecular cage-like compound Download PDFInfo
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Abstract
The invention belongs to the technical field of fine chemical engineering, and relates to a preparation method and application of a binuclear Ir (III) metal-organic supermolecular cage compound. Wherein the preparation method comprises using aliphatic diamine A as a connecting body and using L1、L2The complex is used as a pre-assembled metal-based ligand Ir (III), sodium borohydride is added to reduce Schiff base-C-N-double bond in the obtained cage structure into-CH-NH-, and the compound with the metal-organic cage structure is finally prepared, wherein the synthetic route is as follows: a + L1→A‑L1Or A + L2→A‑L2. The preparation process related by the invention is simple, the design idea is novel, the yield of the target compound is high, and the obtained work isCan be made of materials with stable chemical properties, and the preassembly is easy to modify. As compounds A-L1Or A-L2When the method is applied to oxidizing 1-oxo-2, 3-dihydro-1-indene-2-methyl formate to generate 2-hydroxy-1-oxo-2, 3-dihydro-1-indene-2-methyl carboxylate, the yield reaches 83 percent, and the method is easier to put into practical application.
Description
Technical Field
The invention relates to a preparation method and application of a binuclear Ir (III) metal-organic supermolecular cage compound, belonging to the technical field of fine chemical engineering.
Background
In 1987, professor Lehn and professor Cram have proposed the concept of "supramolecules", a science of studying complex and ordered supramolecular systems with specific structures and functions formed by the combination of two or more chemical species through intermolecular force interactions. Among them, the metal-organic supermolecule cage compound is widely used in the fields of identification, catalysis, stabilization of active substances, drug delivery and the like as a novel molecular crystal material, and has gradually played an important role in chemical industry production.
In 2009, the Nitschke topic reported in the Science journal a water-soluble caged compound that could be used to stabilize active white phosphorus in air; the subject group in the professor of the chapter of Chun has reported an example of "molecular lantern" metal-organic supramolecular compound Ce-DBDS, which can be used for Mg2+Selective identification of (2); professor M.Fujita reports one instance of Pd in journal of Science 20066L4The metal-organic supermolecule compound utilizes octahedral limited cavity to catalyze Diels-Alder reaction stereoselectively. The metal-organic supermolecular cage compound is synthesized by self-assembly mainly through formation of coordination bonds between organic ligands (ligand) and metal ions (metal), and the methods for constructing supermolecular cage structures that have been commonly used so far mainly include: directional bonding strategies, symmetry matching strategies, molecular paneling strategies, bi-metallic construction units, weak connection strategy assembly, and the like. However, the above method also has the following limitations: (1) coordination bond-oriented supramolecular self-assembly processes require the availability of building blocks with specific coordination sites that may be encountered in yieldsLow, difficult synthesis and the like. (2) The specific directionality of coordination bonds and the general involvement of rigid ligands limits the randomness of coordination assembly, resulting in difficulties in synthesizing more complex supramolecular assemblies; (3) the metal coordination mode is relatively fixed, the ligand source is limited, and the assembly change mode is few; (4) the research for designing and synthesizing ligands with specific functions to construct a three-dimensional supramolecular structure to achieve its functionality is currently lacking. It should be noted that the metal-organic cage structure obtained by self-assembly through formation of coordination bonds tends to be very unstable because the cage structure is easily dissociated in solution due to coordination reversibility specific to coordination bonds, and is poor in acid-base resistance and low in yield. Therefore, the development of a novel method capable of efficiently preparing a supramolecular cage-like structure which is stable in structure and easy to synthesize will become one of the research cores in the field.
In the current research, the construction of a supermolecular assembly with a macrocyclic and polyhedral structure taking a polynuclear Ir (III) complex as a center is rarely reported, wherein the difficulty is how to use an Ir (III) complex building block to construct a metal-organic supermolecular structure. The concrete points are as follows: (1) the prior report mainly uses bisphenylpyridine [ Ir (ppy)2]+The remaining two coordination points of the Ir (III) atom in the unit are coordinated and assembled with the second N-containing ligand, and the Ir (III) atom has larger steric hindrance around the atom, so that a complex supermolecular structure is not easy to synthesize; (2) the constructed supermolecular structure has poor stability and is easy to react with solvent molecules (CH)3CN, DMSO, DMF, etc.) resulting in dissociation of the assembly; (3) the construction process is not controllable. Several methods for synthesizing cage compounds based on Ir (III) are reported at present, wherein unstable coordination bond modes are involved.
The present invention addresses the needs of the current research with emphasis on: firstly, a series of metal-organic supermolecular cage-like compounds containing Schiff base bonds are synthesized by utilizing a pre-assembled tripod type metal-based ligand Ir (III) complex and a second ligand aliphatic amine through a dynamic reversible chemical bond mode, so that the problem of uncontrollable construction in the assembling process is solved; secondly, Schiff base-C-N-double bond in the structure is reduced to obtain-CH-NH-, the supermolecule metal-organic cage structure obtained by the method is very stable, and a series of problems of coordination dissociation, poor stability and the like after assembly are solved. Therefore, the method has high research and application values.
The α -hydroxy- β ketoester structural unit widely exists in bioactive substances and natural products and is also an important synthesis precursor of a plurality of medicines.A main way for artificially synthesizing the structure is to construct a β -ketoester compound by catalyzing the formation of C-O bond at α position.Gengwei professor of university of great courseware in 2010 uses Tetraphenylporphyrin (TPP) as a photocatalyst, activated air as an oxidant and a cinchona alkaloid derivative catalyst to successfully catalyze hydroxylation reaction of β -ketoester α. the Shoujin task group in 2017 reports that an oxazoline ligand capable of sensing light and Ni (acac)2The formation of a bifunctional Lewis acid catalyst also accomplishes the above reaction. However, these methods still have problems of high cost, complex catalyst structure, low efficiency, difficult preparation, etc. The binuclear Ir (III) metal-organic supermolecular cage compound can be excited by light to activate triplet oxygen through energy transfer3O2) Producing a highly reactive singlet state (1O2) Can successfully catalyze the α hydroxylation reaction of β -keto ester.
Disclosure of Invention
The metal-organic cage compound prepared by the method has the advantages of excellent photophysical and chemical properties, controllable spatial structure, wide catalytic reaction adaptability and the like, can generate singlet oxygen so that the metal-organic cage compound can efficiently catalyze β -keto ester α hydroxylation reaction, and more importantly, the metal-organic supermolecule target material also has the advantages of simplicity in preparation, low cost of initial raw materials and the like.
To achieve the above object, the present invention solves the problems in the prior artThe technical scheme adopted by the invention is as follows: a process for preparing the binuclear Ir (III) supermolecular metal-organic cage-structured compound from aliphatic diamine A and L1、L2The complex is used as a pre-assembled metal-based ligand Ir (III), sodium borohydride is added to reduce Schiff base-C-N-double bond in the obtained cage structure into-CH-NH-, and the compound with the metal-organic cage structure is finally prepared, wherein the synthetic route is as follows:
A+L1→A-L1or A + L2→A-L2
The aliphatic diamine A is selected from one of trans-1, 2-cyclohexanediamine, 1, 3-propane diamine or 1, 2-ethane diamine;
the preassembled metal-based ligand Ir (III) complex L1Has a molecular formula of C39H30IrN3O6And has the following molecular structural formula (A);
the preassembled metal-based ligand Ir (III) complex L2Has a molecular formula of C54H36IrN3O3And has the following molecular structural formula (B);
the compounds A to L2The preparation method comprises the following steps:
step 1, mixing palladium acetate, 4-bromobenzoic acid and K2CO3According to the following steps: 70-80: 145-155, adding the mixture into a mixture of 300-400 mL with a volume ratio of 3: 1, adding 2-4 mL of 2-bromopyridine into a mixed solvent of ethanol and water, reacting for 1-4 h at 75-85 ℃, cooling to room temperature, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation, wherein the volume ratio is 100: passing petroleum ether and ethyl acetate of 1 through a silica gel column to obtain white powder;
and 2, mixing iridium trichloride and the white powder prepared in the step 1 according to the weight ratio of 1: 2-4, refluxing and stirring for 10-15 hours at 120-130 ℃, performing suction filtration after reaction is finished, washing a filter cake obtained by suction filtration with ethanol, and performing vacuum drying on the washed filter cake to obtain yellow powder;
step 3, adding the yellow powder prepared in the step 2 and silver trifluoromethanesulfonate into 30-40 mL of acetone according to a molar ratio of 1: 1-3, mixing, introducing argon, performing reflux reaction for 3-5 h, performing suction filtration after the reaction is stopped, collecting filtrate, adding the filtrate, 0.5-0.7 mL of triethylamine and 400-600 mg of the white powder prepared in the step 1 into a three-neck flask, introducing argon, performing reflux reaction for 20-30 h, performing reduced pressure distillation after the reaction is finished to remove the solvent, passing dichloromethane through a column, collecting a yellow strip, drying the yellow strip with anhydrous sodium sulfate, and finally performing reduced pressure distillation to remove dichloromethane to obtain yellow powder;
and 4, mixing the yellow powder prepared in the step 3 with p-formyl phenylboron according to the weight ratio of 1: 4-6 mol ratio of the metal base ligand Ir (III) complex L is dissolved in 10-15 mL of THF, argon is introduced for 3 times, 115-125 mg of palladium tetratriphenylphosphine is added to react for 40-50 h at 70-90 ℃, and then dichloromethane is used for extraction and silica gel column passing to obtain red powder, namely the pre-assembled metal base ligand Ir (III) complex L2；
Step 5, pre-assembled metal-based ligand Ir (III) complex L prepared in step 42With aliphatic diamine a in a ratio of 1: 1.2-3, adding the mixture into a reactor with a volume ratio of 2: 1, stirring for 20-30 h at 100-120 ℃, adding 1-2 mg of p-toluenesulfonic acid as a catalyst, after the reaction is finished, filtering off the solvent, washing the solvent for multiple times by using acetonitrile to obtain light yellow powder, dissolving the light yellow powder in 30-40 mL of methanol solution, adding 30mg of sodium borohydride 10 times, stirring and reacting for 20-30 h at 0 ℃ under the protection of nitrogen, washing dichloromethane for multiple times after the reaction is finished, extracting the dichloromethane for multiple times by using anhydrous sodium sulfate, drying the organic phase by using anhydrous sodium sulfate, and evaporating the solvent to dryness by using a rotary method to obtain the target compound A-L2；
The compounds A to L1The preparation method comprises the following steps:
step 1, mixing iridium trichloride and 4- (5-methoxypyridin-2-yl) benzaldehyde according to the weight ratio of 1: 2-4, mixing, and adding into a mixture of 50-70 mL with a volume ratio of 3: 1, refluxing and stirring at 115-125 ℃ for 10-15 hours in a mixed solvent of ethylene glycol and water, performing suction filtration after reaction, washing a filter cake obtained by suction filtration with ethanol, and performing vacuum drying on the washed filter cake to obtain red powder;
step 2, adding 1-2 g of red powder prepared in the step 1 into 70-90 mL of acetonitrile solution, then adding 700-800 mg of silver trifluoromethanesulfonate, reacting at 70-90 ℃ for 1-4 h, after the reaction is finished, performing suction filtration by using kieselguhr to remove AgCl, and then performing reduced pressure distillation to remove the solvent to obtain yellow powder;
and 3, mixing the yellow powder prepared in the step 2 with 4- (5-methoxypyridin-2-yl) benzaldehyde according to the weight ratio of 1: adding 1.2-3 mol ratio of the complex into 20-40 mL of o-dichlorobenzene solution, reacting for 110-130 h at 120-140 ℃, distilling under reduced pressure to remove the solvent after the reaction is finished, passing dichloromethane through a silica gel column to collect red strips, namely the preassembled metal-based ligand Ir (III) complex L1；
Step 4, pre-assembled metal-based ligand Ir (III) complex L prepared in step 31With aliphatic diamine a in a ratio of 1: 1.2-3, adding the mixture into a reactor with a volume ratio of 2: 1, stirring for 20-30 h at 100-120 ℃, adding 1-2 mg of p-toluenesulfonic acid as a catalyst, after the reaction is finished, filtering off the solvent, washing the solvent for multiple times by using acetonitrile to obtain light yellow powder, dissolving the light yellow powder in 30-40 mL of methanol solution, adding 30mg of sodium borohydride 10 times, stirring and reacting for 20-30 h at 0 ℃ under the protection of nitrogen, washing dichloromethane for multiple times after the reaction is finished, extracting the dichloromethane for multiple times by using anhydrous sodium sulfate, drying the organic phase by using anhydrous sodium sulfate, and evaporating the solvent to dryness by using a rotary method to obtain a target compound A-L1。
The compound prepared by the method is applied to catalyzing 1-oxo-2, 3-dihydro-1-indene-2-methyl formate to generate 2-hydroxy-1-oxo-2, 3-dihydro-1-indene-2-methyl carboxylate.
The invention has the beneficial effects that: a preparation method and application of a binuclear Ir (III) metal-organic supermolecular cage compound. Wherein the preparation method comprises using aliphatic diamine A as a connecting body and using L1、L2The complex is used as a pre-assembled metal-based ligand Ir (III), sodium borohydride is added to reduce Schiff base-C-N-double bond in the obtained cage structure into-CH-NH-, and the compound with the metal-organic cage structure is finally prepared, wherein the synthetic route is as follows:A+L1→A-L1or A + L2→A-L2The aliphatic diamine A is selected from one of trans-1, 2-cyclohexanediamine, 1, 3-propanediamine or ethylenediamine; the preassembled metal-based ligand Ir (III) complex L1Has a molecular formula of C39H30IrN3O6The preassembly metal-based ligand Ir (III) complex L2Has a molecular formula of C54H36IrN3O3. By adopting the method, the cage-shaped compound containing Ir (III) dinuclear supermolecules is controllably and efficiently synthesized. The invention takes Ir (III) with fluorescence characteristic as a functional ligand and aliphatic amine to prepare a functional metal-organic cage compound with a specific space structure by a dynamic covalent assembly and reduction immobilization strategy synthesis method. Compared with the prior art, the preparation process related by the invention is simple, the design idea is novel, the yield of the target compound is high, the target compound has the fluorescence characteristic, the obtained functional material has stable chemical property, and the pre-assembly body is easy to modify. As compounds A-L1Or A-L2When the method is applied to oxidizing 1-oxo-2, 3-dihydro-1-indene-2-methyl formate to generate 2-hydroxy-1-oxo-2, 3-dihydro-1-indene-2-methyl carboxylate, the yield reaches 83 percent, and the method is easier to put into practical application.
Drawings
FIG. 1 shows Compounds A to L of example 12Crystal structure of (2).
In the figure: (a) is a positive image of the crystal structure, and (b) is a negative image of the crystal structure.
FIG. 2 shows Compounds A to L of example 12High resolution mass spectra of the solution.
FIG. 3 is the preassembly of the metal-base-ligand Ir (III) complex L of example 12Nuclear magnetic map of (a).
FIG. 4 is a drawing of Compounds A-L of example 12Nuclear magnetic result diagram of catalyzing 1-oxo-2, 3-dihydro-1-indene-2-carboxylic acid methyl ester to generate 2-hydroxy-1-oxo-2, 3-dihydro-1-indene-2-carboxylic acid methyl ester.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Palladium acetate (180mg, 0.8mmol), 4-bromobenzeneboronic acid (12.0g, 60mmol) and K2CO3(16.6g, 120mmol) was added to 300mL of a 3: 1, adding 4mL of 2-bromopyridine into a mixed solvent of ethanol and water, reacting for 1h at 80 ℃, cooling to room temperature, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation by adopting a volume ratio of 100: passing petroleum ether of 1 and ethyl acetate through a silica gel column gave 6g of a white powder in 51% yield. ESI-MS Mass Spectrometry, exact molecular weight 231.988, actual Peak 232.988[ M + H ]]+. Iridium trichloride (900mg, 3mmol) and white powder (1.77g, 7.7mmol) are mixed, the mixture is refluxed and stirred for 10 hours at 120 ℃, after the reaction is finished, suction filtration is carried out, filter cake obtained by suction filtration is washed by ethanol, and the washed filter cake is dried in vacuum to obtain yellow powder-dichloro bridged bromine 1.23g, and the yield is 62%. ESI-MS Mass Spectrometry, exact molecular weight 1439.8309, actual Peak 1440.8309[ M + H ]]+. Adding dichloro-bridged-bromine (0.74g, 1.5mmol) and silver trifluoromethanesulfonate (512mg, 2mmol) into 40mL of acetone for mixing, introducing argon for reflux reaction for 3h, performing suction filtration after the reaction is stopped, collecting filtrate, adding the filtrate, 0.5mL of triethylamine and 400mg of white powder into a three-neck flask, introducing argon for reflux reaction for 24h, performing reduced pressure distillation to remove the solvent after the reaction is finished, passing dichloromethane through a column, collecting a yellow strip, drying the yellow strip by using anhydrous sodium sulfate, and finally performing reduced pressure distillation to remove dichloromethane to obtain yellow powder-mer-Ir-Br 0.55g, wherein the yield is 60%. ESI-MS Mass Spectrometry, exact molecular weight 889.8915, actual Peak 890.8915[ M + H ]]+，912.8813[M+Na]+. mer-Ir-Br (300mg, 0.336mmol) and p-formylphenylboron (450mg, 1.5mmol) are dissolved in 12ml THF, argon is introduced for 3 times, then 120mg palladium tetratriphenylphosphine is added to react for 48h at 80 ℃, and then dichloromethane is used for extracting the mixture through a silica gel column to obtain red powder, namely the preassembled metal-based ligand Ir (III) complex L2150mg, 50% yield, the nuclear magnetic map is shown in FIG. 3. ESI-MS Mass Spectrometry, exact molecular weight 889.8915, actual Peak 967.2386[ M + H ]]+，990.22843[M+Na]+. Preassembling a metal-based ligand Ir (III) complex L2(24mg, 0.024mmol) and trans 1, 2-cyclohexanediamine (4.1mg, 0.036mmol) were added to a volume ratio of 2: 1 mixed solvent of toluene and acetonitrileStirring for 24 hours at 110 ℃, adding 1mg of p-toluenesulfonic acid as a catalyst, after the reaction is finished, filtering off the solvent, washing the solvent for multiple times by using acetonitrile to obtain light yellow powder, dissolving the light yellow powder in a 30mL methanol solution, adding 30mg of sodium borohydride for 10 times, stirring for reaction for 24 hours at 0 ℃ under the protection of nitrogen, after the reaction is finished, washing dichloromethane for multiple times for extraction, drying an organic phase by using anhydrous sodium sulfate, and evaporating the solvent to dryness by rotation to obtain target compounds A-L225mg, 72% yield, crystal structure of the target compound as shown in FIG. 1, and high resolution mass spectrum as shown in FIG. 2. ESI-MS Mass Spectrometry, exact molecular weight 2168.7608, actual Peak 2169.7653[ M + H ]]+，1085.3859[M+2H]2+。
Example 2
The preassembled metal-based ligand Ir (III) complex L prepared in example 12(24mg, 0.024mmol) and 1, 3-propanediamine (3mg,0.0375mmol) were added to a volume ratio of 2: 1, stirring for 24 hours at 110 ℃, adding 1mg of p-toluenesulfonic acid as a catalyst, after the reaction is finished, filtering off the solvent, washing the solvent for multiple times by using acetonitrile to obtain light yellow powder, dissolving the light yellow powder in 30mL of methanol solution, adding 30mg of sodium borohydride for 10 times, stirring for reaction for 24 hours at 0 ℃ under the protection of nitrogen, after the reaction is finished, washing dichloromethane for multiple times by using water, drying an organic phase by using anhydrous sodium sulfate, and evaporating the solvent to dryness by rotation to obtain target compounds A-L217mg, yield 64%, ESI-MS Mass Spectrometry M/z 1952.319[ M + H ]]+。
Example 3
The preassembled metal-based ligand Ir (III) complex L prepared in example 12Adding (24mg, 0.024mmol) and 1, 2-ethanediamine ((2.25mg,0.0375mmol) into a mixed solvent of toluene and acetonitrile with a volume ratio of 2: 1, stirring for 24h at 110 ℃, adding 1mg of p-toluenesulfonic acid as a catalyst, washing the solvent after the reaction is finished with the acetonitrile for multiple times to obtain light yellow powder, dissolving the light yellow powder in 30mL of methanol solution, adding 30mg of sodium borohydride for 10 times, stirring for reaction for 24h at 0 ℃ under the protection of nitrogen, washing dichloromethane after the reaction is finished, extracting for multiple times, and removing waterDrying the organic phase with sodium sulfate, and evaporating the solvent to obtain target compounds A-L218mg, yield 68%, ESI-MS Mass Spectrometry M/z 1898.6572[ M + H ]]+。
Example 4
Iridium trichloride (1.2mg, 4mmol) was mixed with 4- (5-methoxypyridin-2-yl) benzaldehyde (2.132g, 10mmol) and added to 60mL of a mixture of 3: 1, refluxing and stirring at 120 ℃ for 10 hours, performing suction filtration after the reaction is finished, washing a filter cake obtained by the suction filtration with ethanol, and drying the washed filter cake in vacuum to obtain 2g of red powder with the yield of 75%. ESI-MS Mass Spectrometry, exact molecular weight 1304.1482, actual Peak 1327.1482[ M + Na [ ]]+. The obtained red powder (1.3g, 1mmol) was added to 80mL of acetonitrile solution, followed by addition of silver trifluoromethanesulfonate (773mg, 13mmol), reaction at 80 ℃ for 4 hours, after completion of the reaction, AgCl was removed by suction filtration with celite, and then the solvent was distilled off under reduced pressure to obtain 1.38g of yellow powder in 67% yield. ESI-MS Mass Spectrometry, exact molecular weight 699.1583, actual Peak 700.1583[ M + H ]]+. Adding the prepared yellow powder (600mg, 0.706mmol) and 4- (5-methoxypyridin-2-yl) benzaldehyde (197mg, 0.92mmol) into 30mL of o-dichlorobenzene solution, reacting at 130 ℃ for 120h, distilling under reduced pressure to remove the solvent after the reaction is finished, passing dichloromethane through a silica gel column to collect a red strip, namely a preassembled metal-based ligand Ir (III) complex L1400mg, yield 68%. ESI-MS Mass Spectrometry, exact molecular weight 829.1764, actual Peak 830.1764M + H]+. The prepared preassembly metal-based ligand Ir (III) complex L1And 1, 2-ethylenediamine (2.25mg,0.0375mmol) to a volume ratio of 2: 1, stirring for 24 hours at 110 ℃, then adding 1mg of p-toluenesulfonic acid as a catalyst, after the reaction is finished, filtering off the solvent, washing the solvent for multiple times by using acetonitrile to obtain light yellow powder, dissolving the light yellow powder in 30mL of methanol solution, adding 30mg of sodium borohydride for 10 times, stirring and reacting for 24 hours under the condition of nitrogen protection and 0 ℃, after the reaction is finished, washing dichloromethane for multiple times by using water, drying an organic phase by using anhydrous sodium sulfate, and evaporating the solvent to dryness by rotation to obtain a target compound A-L115 mg, yield 68%. ESI-MS Mass Spectrometry:m/z:1731.5928[M+H]+。
Example 5
The preassembled metal-based ligand Ir (III) complex L prepared in example 41(21mg, 0.025mmol) and 1,3 propanediamine (3mg,0.0375mmol) were added to a volume ratio of 2: 1, stirring for 24 hours at 110 ℃, then adding 1mg of p-toluenesulfonic acid as a catalyst, after the reaction is finished, filtering off the solvent, washing the solvent for multiple times by using acetonitrile to obtain light yellow powder, dissolving the light yellow powder in 30mL of methanol solution, adding 30mg of sodium borohydride for 10 times, stirring and reacting for 24 hours under the condition of nitrogen protection and 0 ℃, after the reaction is finished, washing dichloromethane for multiple times by using water, drying an organic phase by using anhydrous sodium sulfate, and evaporating the solvent to dryness by rotation to obtain a target compound A-L118mg, yield 75%. ESI-MS Mass Spectrometry M/z 1773.7428[ M + H ]]+。
Example 6
The preassembled metal-based ligand Ir (III) complex L prepared in example 41(21mg, 0.025mmol) and trans 1, 2-cyclohexanediamine (4.1mg, 0.036mmol) were added to a volume ratio of 2: 1, stirring for 24 hours at 110 ℃, then adding 1mg of p-toluenesulfonic acid as a catalyst, after the reaction is finished, filtering off the solvent, washing the solvent for multiple times by using acetonitrile to obtain light yellow powder, dissolving the light yellow powder in 30mL of methanol solution, adding 30mg of sodium borohydride for 10 times, stirring and reacting for 24 hours under the condition of nitrogen protection and 0 ℃, after the reaction is finished, washing dichloromethane for multiple times by using water, drying an organic phase by using anhydrous sodium sulfate, and evaporating the solvent to dryness by rotation to obtain a target compound A-L116mg, yield 68%. ESI-MS Mass Spectrometry M/z 1893.7728[ M + H ]]+。
Example 7
The substrate methyl 1-oxo-2, 3-dihydro-1-indene-2-carboxylate (19.1mg, 0.1mmol), the compound A-L prepared in example 12(5mg), a dichloromethane solution (5mL) and nickel acetylacetonate (0.02mmol, 3.41mg) were charged into a photoreaction tube, which was then placed under an oxygen atmosphere and illuminated with an LED lamp having a wavelength of 420nm for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and the catalytic product 2-hydroxy-1-oxo is obtained by passing through a silica gel column by using petroleum ether-2, 3-dihydro-1-indene-2-carboxylic acid methyl ester 17mg, yield 83%. The reaction conversion was calculated by taking the appropriate amount of product and performing a nuclear magnetic test, the nuclear magnetic results of which are shown in fig. 4.
Claims (2)
1. A preparation method of a binuclear Ir (III) supermolecular metal-organic cage-structured compound is characterized by comprising the following steps: with aliphatic diamine A as linker and L1、L2The complex is used as a pre-assembled metal-based ligand Ir (III), sodium borohydride is added to reduce Schiff base-C-N-double bond in the obtained cage structure into-CH-NH-, and the compound with the metal-organic cage structure is finally prepared, wherein the synthetic route is as follows:
A+L1→A-L1or A + L2→A-L2
The aliphatic diamine A is selected from one of trans-1, 2-cyclohexanediamine, 1, 3-propane diamine or 1, 2-ethane diamine;
the preassembled metal-based ligand Ir (III) complex L1Has a molecular formula of C39H30IrN3O6And has the following molecular structural formula (A);
the preassembled metal-based ligand Ir (III) complex L2Has a molecular formula of C54H36IrN3O3And has the following molecular structural formula (B);
the compounds A to L2The preparation method comprises the following steps:
step 1, mixing palladium acetate, 4-bromobenzoic acid and K2CO3According to the following steps: 70-80: 145-155, adding the mixture into a mixture of 300-400 mL with a volume ratio of 3: 1, adding 2-4 mL of 2-bromopyridine into a mixed solvent of ethanol and water, reacting for 1-4 h at 75-85 ℃, cooling to room temperature, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation, wherein the volume ratio is 100: passing petroleum ether and ethyl acetate of 1 through a silica gel column to obtain white powder;
and 2, mixing iridium trichloride and the white powder prepared in the step 1 according to the weight ratio of 1: 2-4, refluxing and stirring for 10-15 hours at 120-130 ℃, performing suction filtration after reaction is finished, washing a filter cake obtained by suction filtration with ethanol, and performing vacuum drying on the washed filter cake to obtain yellow powder;
step 3, adding the yellow powder prepared in the step 2 and silver trifluoromethanesulfonate into 30-40 mL of acetone according to a molar ratio of 1: 1-3, mixing, introducing argon, performing reflux reaction for 3-5 h, performing suction filtration after the reaction is stopped, collecting filtrate, adding the filtrate, 0.5-0.7 mL of triethylamine and 400-600 mg of the white powder prepared in the step 1 into a three-neck flask, introducing argon, performing reflux reaction for 20-30 h, performing reduced pressure distillation after the reaction is finished to remove the solvent, passing dichloromethane through a column, collecting a yellow strip, drying the yellow strip with anhydrous sodium sulfate, and finally performing reduced pressure distillation to remove dichloromethane to obtain yellow powder;
and 4, mixing the yellow powder prepared in the step 3 with p-formyl phenylboron according to the weight ratio of 1: 4-6 mol ratio of the metal base ligand Ir (III) complex L is dissolved in 10-15 mL of THF, argon is introduced for 3 times, 115-125 mg of palladium tetratriphenylphosphine is added to react for 40-50 h at 70-90 ℃, and then dichloromethane is used for extraction and silica gel column passing to obtain red powder, namely the pre-assembled metal base ligand Ir (III) complex L2；
Step 5, pre-assembled metal-based ligand Ir (III) complex L prepared in step 42With aliphatic diamine a in a ratio of 1: 1.2-3, adding the mixture into a reactor with a volume ratio of 2: 1, stirring for 20-30 h at 100-120 ℃, adding 1-2 mg of p-toluenesulfonic acid as a catalyst, after the reaction is finished, filtering off the solvent, washing the solvent for multiple times by using acetonitrile to obtain light yellow powder, dissolving the light yellow powder in 30-40 mL of methanol solution, adding 30mg of sodium borohydride 10 times, stirring and reacting for 20-30 h at 0 ℃ under the protection of nitrogen, washing dichloromethane for multiple times after the reaction is finished, extracting the dichloromethane for multiple times by using anhydrous sodium sulfate, drying the organic phase by using anhydrous sodium sulfate, and evaporating the solvent to dryness by using a rotary method to obtain the target compound A-L2；
The compounds A to L1The preparation method comprises the following steps:
step 1, mixing iridium trichloride and 4- (5-methoxypyridin-2-yl) benzaldehyde according to the weight ratio of 1: 2-4, mixing, and adding into a mixture of 50-70 mL with a volume ratio of 3: 1, refluxing and stirring at 115-125 ℃ for 10-15 hours in a mixed solvent of ethylene glycol and water, performing suction filtration after reaction, washing a filter cake obtained by suction filtration with ethanol, and performing vacuum drying on the washed filter cake to obtain red powder;
step 2, adding 1-2 g of red powder prepared in the step 1 into 70-90 mL of acetonitrile solution, then adding 700-800 mg of silver trifluoromethanesulfonate, reacting at 70-90 ℃ for 1-4 h, after the reaction is finished, performing suction filtration by using kieselguhr to remove AgCl, and then performing reduced pressure distillation to remove the solvent to obtain yellow powder;
and 3, mixing the yellow powder prepared in the step 2 with 4- (5-methoxypyridin-2-yl) benzaldehyde according to the weight ratio of 1: adding 1.2-3 mol ratio of the complex into 20-40 mL of o-dichlorobenzene solution, reacting for 110-130 h at 120-140 ℃, distilling under reduced pressure to remove the solvent after the reaction is finished, passing dichloromethane through a silica gel column to collect red strips, namely the preassembled metal-based ligand Ir (III) complex L1；
Step 4, pre-assembled metal-based ligand Ir (III) complex L prepared in step 31With aliphatic diamine a in a ratio of 1: 1.2-3, adding the mixture into a reactor with a volume ratio of 2: 1, stirring for 20-30 h at 100-120 ℃, adding 1-2 mg of p-toluenesulfonic acid as a catalyst, after the reaction is finished, filtering off the solvent, washing the solvent for multiple times by using acetonitrile to obtain light yellow powder, dissolving the light yellow powder in 30-40 mL of methanol solution, adding 30mg of sodium borohydride 10 times, stirring and reacting for 20-30 h at 0 ℃ under the protection of nitrogen, washing dichloromethane for multiple times after the reaction is finished, extracting the dichloromethane for multiple times by using anhydrous sodium sulfate, drying the organic phase by using anhydrous sodium sulfate, and evaporating the solvent to dryness by using a rotary method to obtain a target compound A-L1。
2. Use of a compound prepared according to the process of claim 1 for catalyzing the formation of methyl 2-hydroxy-1-oxo-2, 3-dihydro-1-indene-2-carboxylate from methyl 1-oxo-2, 3-dihydro-1-indene-2-carboxylate.
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