Preparation method and application of binuclear Ir (III) metal-organic supramolecular cage compound

A supramolecular, organic cage technology, applied in the preparation of organic compounds, organic compound/hydride/coordination complex catalysts, organic chemistry and other directions, can solve the problems of preparation difficulties, synthesis difficulties, fixed metal coordination methods, etc. Achieve the effect of simple preparation process, stable chemical properties and novel design ideas

Active Publication Date: 2020-05-15
DALIAN UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the above method also has the following limitations: (1) The coordination bond-directed supramolecular self-assembly process needs to obtain building blocks with specific coordination sites, and the introduction of coordination sites may encounter low yields, Difficulties in synthesis, etc.
(2) The unique directionality of the coordination bond and the generally rigid ligands involved limit the randomness of the coordination assembly, making it difficult to synthesize more complex supramolecular assemblies; (3) the metal coordination The way is relatively fixed, the sources of ligands are limited, and the ways of assembly changes are few; (4) The research on designing and synthesizing ligands with special energy functions to construct three-dimensional supramolecular structures to achieve their functionality is still relatively lacking.
However, these methods still have some problems, such as high cost, complex catalyst structure, low efficiency, and difficult preparation.

Method used

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  • Preparation method and application of binuclear Ir (III) metal-organic supramolecular cage compound
  • Preparation method and application of binuclear Ir (III) metal-organic supramolecular cage compound
  • Preparation method and application of binuclear Ir (III) metal-organic supramolecular cage compound

Examples

Experimental program
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Effect test

Embodiment 1

[0034] Palladium acetate (180mg, 0.8mmol), 4-bromophenylboronic acid (12.0g, 60mmol) and K 2 CO 3 (16.6g, 120mmol) was added to 300mL of a mixed solvent of ethanol and water with a volume ratio of 3:1, and then 4mL of 2-bromopyridine was added to react at 80°C for 1h, cooled to room temperature, extracted with ethyl acetate, anhydrous Dry over sodium sulfate, filter and rotary evaporate, and use petroleum ether and ethyl acetate with a volume ratio of 100:1 to pass through a silica gel column to obtain 6 g of white powder with a yield of 51%. ESI-MS mass spectrum, exact molecular weight 231.988, actual peak 232.988[M+H] + . Mix iridium trichloride (900mg, 3mmol) with white powder (1.77g, 7.7mmol), reflux and stir at 120°C for 10h, after the reaction is completed, filter with suction and wash the obtained filter cake with ethanol, and vacuum dry the washed Filter cake to obtain yellow powder - 1.23 g of dichloro-bridged bromine, with a yield of 62%. ESI-MS mass spectrum, ex...

Embodiment 2

[0036] The pre-assembled metal-based ligand Ir(III) complex L prepared in Example 1 2 (24mg, 0.024mmol) and 1,3 propylenediamine (3mg, 0.0375mmol) were added to a mixed solvent of toluene and acetonitrile with a volume ratio of 2:1, stirred at 110°C for 24h, and then added 1mg of p-toluenesulfonate The acid is used as the catalyst. After the reaction, the solvent is filtered off by suction and washed with acetonitrile for many times to obtain a light yellow powder. Stir the reaction at 0°C for 24 hours, wash with water and extract with dichloromethane several times after the reaction, dry the organic phase with anhydrous sodium sulfate, and evaporate the solvent to obtain the target compound A-L 2 17 mg, yield 64%, ESI-MS mass spectrum: m / z: 1952.319[M+H] + .

Embodiment 3

[0038] The pre-assembled metal-based ligand Ir(III) complex L prepared in Example 1 2 (24mg, 0.024mmol) and 1,2 ethylenediamine ((2.25mg, 0.0375mmol) were added to a mixed solvent of toluene and acetonitrile with a volume ratio of 2:1, stirred at 110°C for 24h, and then 1mg of p- Toluenesulfonic acid is used as a catalyst. After the reaction, the solvent is filtered off by suction and washed with acetonitrile for several times to obtain a light yellow powder. Then the light yellow powder is dissolved in 30 mL of methanol solution, and then 30 mg of sodium borohydride is added in 10 times. Stir the reaction under nitrogen protection at 0°C for 24 hours. After the reaction is completed, wash with dichloromethane and extract several times, dry the organic phase with anhydrous sodium sulfate, and rotary evaporate to dryness to obtain the target compound A-L 2 18mg, yield 68%, ESI-MS mass spectrum: m / z: 1898.6572[M+H] + .

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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 supramolecular cage compound. According to the preparation method, aliphatic diamine A is used as a connecting body; L1 and L2 are used as pre-assembled metal-based ligand Ir (III) complexes, then sodium borohydride is added to reduceSchiff base -C=N- double bonds in the obtained cage structure into -CH-NH-, finally, the compound with the metal-organic cage structure is prepared, and the synthetic route of the compound is: A+L1 toA-L1 or A+L2 to A-L2. The preparation process is simple, the design idea is novel, the yield of the target compound is high, the obtained functional material is stable in chemical property, and the pre-assembled body is easy to modify. The compound A-L1 or A-L2 is used in oxidation of 1-oxo-2,3-dihydro-1-indene-2-methyl formate to generate 2-hydroxy-1-oxo-2,3-dihydro-1-indene-2-methyl carboxyl ate, the yield is as high as 83%, and the compound A-L1 or A-L2 is easier to put into practical application.

Description

technical field [0001] The invention relates to a preparation method and application of a binuclear Ir(III) metal-organic supramolecular cage compound, belonging to the technical field of fine chemicals. Background technique [0002] In 1987, Professor Lehn and Professor Cram proposed the concept of "supramolecules", which is to study complex and ordered supramolecules with specific structures and functions formed by the combination of two or more chemical species through the interaction of intermolecular forces A science of systems. Among them, metal-organic supramolecular cage compounds, as a new type of molecular crystal materials, are widely used in the fields of identification, catalysis, stabilization of active substances and drug delivery, and have gradually played an important role in the production of chemical industry. [0003] In 2009, Nitschke's research group reported a water-soluble cage compound in Science magazine, which can be used to stabilize active white...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G83/00B01J31/22C07C67/31C07C69/757
CPCB01J31/1691B01J31/1815B01J2231/70B01J2531/827C07C67/31C08G83/008C07C2602/08C07C69/757
Inventor 何成李震康李学召吴金国
Owner DALIAN UNIV OF TECH
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