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CN111154115B - 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 PDF

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CN111154115B
CN111154115B CN202010004115.3A CN202010004115A CN111154115B CN 111154115 B CN111154115 B CN 111154115B CN 202010004115 A CN202010004115 A CN 202010004115A CN 111154115 B CN111154115 B CN 111154115B
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何成
李震康
李学召
吴金国
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Dalian University of Technology
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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, the obtained functional material has stable chemical properties, 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.

Description

Preparation method and application of binuclear Ir (III) metal-organic supermolecular cage-like compound
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) the coordination bond-oriented supramolecular self-assembly process needs to obtain a building unit with a specific coordination site, and the introduction of the coordination site can cause the problems of low yield, 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.
The current research has very few reports on the construction of macrocyclic and polyhedral supramolecular assemblies with polynuclear Ir (III) complexes as centers, wherein the difficulty is how to use Ir (III) complex building blocks to construct metal-organic supramolecular junctionsAnd (5) forming. 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 construction of complex compounds using visible light catalysis strategy has been an important approach in organic synthesis, but the direct participation of visible light activated molecular oxygen in the construction of C-O bond remains a huge challenge. The extensive presence of α -hydroxy- β ketoester building blocks in biologically active substances and natural products is also an important synthetic precursor for many drugs. At present, the main way for artificially synthesizing the structure is to construct a beta-keto ester compound by catalyzing the formation of a C-O bond at the alpha position. The beta-keto ester alpha hydroxylation reaction is successfully catalyzed by using a cinchona alkaloid derivative catalyst by using Tetraphenylporphyrin (TPP) as a photocatalyst and activated air as an oxidant in the professor of Mengqing, university of great connective engineering in 2010. The 2017 Xiaowenjing problem group reports photosensitive oxazoline ligand 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 and catalystComplex structure, low efficiency, difficult preparation and the like. 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 alpha hydroxylation reaction of beta-keto ester.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method and application of a binuclear Ir (III) metal-organic supermolecular cage compound. The metal-organic cage-shaped compound prepared by the method has excellent photophysical and chemical properties; the space structure is controllable; the catalytic reaction has the advantages of wide adaptability and the like; and the ability to generate singlet oxygen, so that the beta-ketoester alpha hydroxylation reaction can be efficiently catalyzed; more importantly, the invention relates to a metal-organic supermolecular target material which also has the advantages of simple preparation, cheap initial raw materials and the like.
In order to achieve the above purpose and solve the problems in the prior art, the invention adopts the following technical scheme: 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);
Figure BDA0002354594850000041
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 ℃, then adding 1-2 mg of p-toluenesulfonic acid as a catalyst,after the reaction is finished, washing the solvent which is removed by suction filtration 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 for 10 times, stirring and reacting for 20-30 h under the condition of nitrogen protection and 0 ℃, washing dichloromethane after the reaction is finished for multiple times, drying an organic phase by using anhydrous sodium sulfate, and evaporating the solvent by rotation 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-L2Oxidation of 1-oxo-2, 3-dihydro-1-indene-2-carboxylic acid methyl ester to give 2-hydroxyThe application of the (E) -1-oxo-2, 3-dihydro-1-indene-2-carboxylic acid methyl ester has the yield of 83 percent and 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 bridging-bromine (0.74g, 1.5mmol) and silver trifluoromethanesulfonate (512mg, 2mmol) into 40mL of acetone, mixing, introducing argon, refluxing for reaction for 3h, suction-filtering after the reaction is stopped, collecting filtrate, and mixing the filtrate, 0.5mL of triethylamine and 400mg of white triethylamineAdding the powder into a three-neck flask, introducing argon, refluxing and reacting for 24 hours, distilling under reduced pressure to remove the solvent after the reaction is finished, passing through a dichloromethane column, collecting a yellow strip, drying by using anhydrous sodium sulfate, and finally distilling under reduced pressure to remove dichloromethane to obtain yellow powder-mer-Ir-Br 0.55g with the yield of 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, 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-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, and cleaning with acetonitrileWashing 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 and reacting for 24 hours under the condition of nitrogen protection and 0 ℃, washing dichloromethane for multiple times after the reaction is finished, drying an organic phase by using anhydrous sodium sulfate, and evaporating the solvent by rotation to obtain a target compound 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 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 for multiple times, drying an organic phase with anhydrous sodium sulfate, and evaporating the solvent to dryness in a rotary manner to obtain a target compound 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 ]]+. The resulting yellow powder (600mg, 0.706mmol) was mixed withAdding 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 silica gel column to collect red bands, namely the 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 toThe volume ratio is 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-2, 3-dihydro-1-indene-2-carboxylic acid methyl ester 17mg is obtained by passing through a silica gel column by using petroleum ether, wherein the yield is 83 percent. 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)

1.一种双核Ir(Ⅲ)金属-有机超分子笼状化合物的制备方法，其特征在于：以脂肪二胺A作为连接体，以L1、L2作为预组装金属基配体Ir(III)配合物，再加入硼氢化钠将所得笼状结构中的席夫碱-C＝N-双键还原为-CH-NH-，最终制得金属-有机笼状结构的化合物，其合成路线如下：1. a preparation method of a binuclear Ir(III) metal-organic supramolecular cage compound, is characterized in that: with aliphatic diamine A as linker, with L 1 , L 2 as pre-assembled metal-based ligand Ir(III ) complex, and then adding sodium borohydride to reduce the Schiff base-C=N- double bond in the obtained cage structure to -CH-NH-, and finally obtain the compound of metal-organic cage structure, and its synthetic route is as follows : A+L1→A-L1或A+L2→A-L2 A+L 1 → AL 1 or A+L 2 → AL 2 所述脂肪二胺A选自反式-1,2-环己二胺，1,3-丙二胺或1，2乙二胺中的一种；The aliphatic diamine A is selected from one of trans-1,2-cyclohexanediamine, 1,3-propanediamine or 1,2 ethylenediamine; 所述预组装金属基配体Ir(III)配合物L1的分子式为C39H33IrN3O6并具有如下(A)分子结构式；The molecular formula of the pre-assembled metal-based ligand Ir(III) complex L 1 is C 39 H 33 IrN 3 O 6 and has the following (A) molecular structural formula; 所述预组装金属基配体Ir(III)配合物L2的分子式为C54H39IrN3O3并具有如下(B)分子结构式；The molecular formula of the pre-assembled metal-based ligand Ir(III) complex L 2 is C 54 H 39 IrN 3 O 3 and has the following (B) molecular structural formula;
Figure FDA0002985894300000011
Figure FDA0002985894300000011
 所述化合物A-L2的制备方法包括以下步骤：The preparation method of the compound AL 2 comprises the following steps: 步骤1、将醋酸钯、4-溴苯硼酸及K2CO3按1：70～80：145～155的摩尔比加入到300～400mL体积比为3：1的乙醇与水的混合溶剂中，再加入2～4mL 2-溴吡啶75～85℃条件下反应1～4h，冷却至室温，用乙酸乙酯萃取，无水硫酸钠干燥，过滤旋蒸，采用体积比为100：1的石油醚与乙酸乙酯过硅胶柱得到白色粉末；Step 1. Add palladium acetate, 4-bromophenylboronic acid and K 2 CO 3 into 300-400 mL of a mixed solvent of ethanol and water with a volume ratio of 3:1 at a molar ratio of 1:70-80:145-155, Then add 2-4 mL of 2-bromopyridine and react at 75-85 °C for 1-4 h, cool to room temperature, extract with ethyl acetate, dry with anhydrous sodium sulfate, filter and rotate, and use petroleum ether with a volume ratio of 100:1. Pass through silica gel column with ethyl acetate to obtain white powder; 步骤2、将三氯化铱与步骤1制得的白色粉末按1：2～4的摩尔比混合，在120～130℃条件下回流搅拌10～15h，反应结束后抽滤并用乙醇洗涤抽滤所得滤饼，真空干燥洗涤后的滤饼，得到黄色粉末；Step 2. Mix iridium trichloride and the white powder obtained in step 1 in a molar ratio of 1:2 to 4, reflux and stir at 120 to 130 ° C for 10 to 15 hours, and after the reaction is completed, suction filtration and wash with ethanol and suction filtration The obtained filter cake is vacuum-dried and washed to obtain a yellow powder; 步骤3、将步骤2制得的黄色粉末与三氟甲烷磺酸银按1:1～3的摩尔比加入到30～40mL丙酮中混合，通入氩气回流反应3～5h，反应停止后抽滤，收集滤液，再将滤液、0.5～0.7mL三乙胺及400～600mg步骤1制得的白色粉末加入到三口烧瓶中，通入氩气回流反应20～30h，待反应结束后减压蒸馏除去溶剂，用二氯甲烷过柱，收集黄色条带，并用无水硫酸钠干燥，最后减压蒸馏除去二氯甲烷得到黄色粉末；Step 3. Add the yellow powder obtained in step 2 and silver trifluoromethanesulfonate in a molar ratio of 1:1 to 3 into 30 to 40 mL of acetone and mix, pass argon back into the reaction for 3 to 5 hours, and pump the reaction after the reaction stops. Filter, collect the filtrate, then add the filtrate, 0.5-0.7 mL of triethylamine and 400-600 mg of the white powder obtained in step 1 into a three-necked flask, pass argon back into the reaction for 20-30 hours, and distill under reduced pressure after the reaction is over Remove the solvent, pass through the column with dichloromethane, collect the yellow band, and dry it with anhydrous sodium sulfate, and finally remove the dichloromethane by distillation under reduced pressure to obtain a yellow powder; 步骤4、将步骤3制得的黄色粉末与对甲酰基苯硼按1：4～6的摩尔比溶于10～15mL的THF中，通入氩气3次，然后加入115～125mg的四三苯基膦钯在70～90℃条件下反应40～50h，然后用二氯甲烷萃取过硅胶柱得到了红色粉末，即预组装金属基配体Ir(III)配合物L2；Step 4. Dissolve the yellow powder obtained in step 3 and p-formyl phenylboron in 10-15 mL of THF at a molar ratio of 1:4-6, pass argon for 3 times, and then add 115-125 mg of tetramine Phenylphosphine palladium was reacted at 70～90℃ for 40～50h, and then extracted with dichloromethane through silica gel column to obtain red powder, namely pre-assembled metal-based ligand Ir(III) complex L 2 ; 步骤5、将步骤4制得的预组装金属基配体Ir(III)配合物L2与脂肪二胺A按1：1.2～3的摩尔比加入到体积比为2：1的甲苯与乙腈的混合溶剂中，100～120℃条件下搅拌20～30h，再加入1～2mg的对甲苯磺酸为催化剂，反应结束后将抽滤掉溶剂用乙腈清洗多次得到淡黄色粉末，再将淡黄色粉末溶于30～40mL甲醇的溶液中，再把30mg的硼氢化钠分10次加进去，在氮气保护0℃条件下搅拌反应20～30h，待反应结束后用水洗二氯甲烷萃取多次，无水硫酸钠干燥有机相，旋蒸干溶剂，得到目标化合物A-L2；Step 5. Add the pre-assembled metal-based ligand Ir(III) complex L 2 prepared in step 4 and aliphatic diamine A into a mixture of toluene and acetonitrile with a volume ratio of 2:1 at a molar ratio of 1:1.2 to 3. In the mixed solvent, stir at 100～120℃ for 20～30h, then add 1～2mg of p-toluenesulfonic acid as a catalyst, after the reaction, filter off the solvent and wash it with acetonitrile for several times to obtain light yellow powder, and then add light yellow powder. The powder was dissolved in 30-40 mL methanol solution, then 30 mg of sodium borohydride was added in 10 times, and the reaction was stirred for 20-30 h under nitrogen protection at 0 °C. The organic phase was dried over anhydrous sodium sulfate, and the solvent was evaporated to dryness to obtain the target compound AL 2 ; 所述化合物A-L1的制备方法包括以下步骤：The preparation method of the compound AL 1 comprises the following steps: 步骤1、将三氯化铱与4-(5-甲氧基吡啶-2-基)苯甲醛按1：2～4的摩尔比混合后加入到50～70mL体积比为3：1的乙二醇与水的混合溶剂中，在115～125℃条件下回流搅拌10～15h，反应结束后抽滤并用乙醇洗涤抽滤所得滤饼，真空干燥洗涤后的滤饼，得到红色粉末；Step 1. Mix iridium trichloride and 4-(5-methoxypyridin-2-yl)benzaldehyde in a molar ratio of 1:2 to 4 and add them to 50 to 70 mL of ethylene glycol with a volume ratio of 3:1. In a mixed solvent of alcohol and water, reflux and stir at 115-125°C for 10-15 hours, after the reaction is completed, suction filtration and wash the filter cake obtained by suction filtration with ethanol, and vacuum dry the washed filter cake to obtain a red powder; 步骤2、将步骤1制得的1～2g的红色粉末加入到70～90mL的乙腈溶液中，随后加入700～800mg的三氟甲烷磺酸银,70～90℃条件下反应1～4h，待反应结束后用硅藻土抽滤除去AgCl，然后减压蒸馏除去溶剂得到黄色粉末；Step 2. Add 1-2 g of the red powder obtained in step 1 to 70-90 mL of acetonitrile solution, then add 700-800 mg of silver trifluoromethanesulfonate, and react at 70-90 °C for 1-4 h, wait for After the reaction, the AgCl was removed by diatomaceous earth suction filtration, and then the solvent was distilled off under reduced pressure to obtain a yellow powder; 步骤3、将步骤2制得的黄色粉末与4-(5-甲氧基吡啶-2-基)苯甲醛按1：1.2～3的摩尔比加入到20～40mL的邻二氯苯溶液中，120～140℃条件下反应110～130h，待反应结束后，减压蒸馏除去溶剂，用二氯甲烷过硅胶柱收集红色条带，即预组装金属基配体Ir(III)配合物L1；Step 3. Add the yellow powder obtained in step 2 and 4-(5-methoxypyridin-2-yl)benzaldehyde into 20-40 mL of o-dichlorobenzene solution at a molar ratio of 1:1.2-3, The reaction is carried out at 120-140°C for 110-130 h, after the reaction is completed, the solvent is distilled off under reduced pressure, and the red band is collected by passing through a silica gel column with dichloromethane, that is, the pre-assembled metal-based ligand Ir(III) complex L 1 ; 步骤4、将步骤3制得的预组装金属基配体Ir(III)配合物L1与脂肪二胺A按1：1.2～3的摩尔比加入到体积比为2：1的甲苯与乙腈的混合溶剂中，100～120℃条件下搅拌20～30h，然后加入1～2mg的对甲苯磺酸为催化剂，反应结束后将抽滤掉溶剂用乙腈清洗多次得到淡黄色粉末，再将淡黄色粉末溶于30～40mL甲醇的溶液中，再把30mg的硼氢化钠分10次加进去，在氮气保护0℃条件下搅拌反应20～30h，待反应结束后用水洗二氯甲烷萃取多次，无水硫酸钠干燥有机相，旋蒸干溶剂，得到目标化合物A-L1。Step 4. Add the pre-assembled metal-based ligand Ir(III) complex L 1 prepared in step 3 and aliphatic diamine A into a mixture of toluene and acetonitrile with a volume ratio of 2:1 at a molar ratio of 1:1.2-3. In the mixed solvent, stir at 100～120℃ for 20～30h, then add 1～2mg of p-toluenesulfonic acid as a catalyst, after the reaction, filter off the solvent and wash it with acetonitrile for several times to obtain light yellow powder, and then add light yellow powder. The powder was dissolved in 30-40 mL methanol solution, then 30 mg of sodium borohydride was added in 10 times, and the reaction was stirred for 20-30 h under nitrogen protection at 0 °C. The organic phase was dried over anhydrous sodium sulfate, and the solvent was evaporated to dryness by rotary evaporation to obtain the target compound AL 1 . 2.根据权利要求1所述方法制备的化合物在催化1-氧代-2,3-二氢-1-茚-2-甲酸甲酯生成2-羟基-1-氧代-2,3-二氢-1-茚-2-羧酸甲酯方面中的应用。2. the compound prepared according to the method of claim 1 generates 2-hydroxyl-1-oxo-2,3-dihydro-1-oxo-2,3-dihydro-1-indene-2-methyl formate in catalysis Hydrogen-1-indene-2-carboxylic acid methyl ester.
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