The Self-assembly And Properties Of Metal-organic Cage Compounds Containing Ir(?)complex

Supramolecular chemistry is a type of science that studies the interaction between molecules.As an important component of supramolecular systems,metal-organic cage compounds are not only favored by chemists because of their elegant aesthetic structure,but more importantly,their promising application prospects.Metal-organic cage compounds have been widely used in the fields of small molecule recognition,catalysis,gas transportation,and drug transportation.Cyclometallic iridium complexes are widely used in photocatalysis and photoelectrochemical cells due to their special photophysical properties such as large Stoke shift,adjustable light absorption and emission,high phosphorescence quantum yield and high quantum efficiency Emitters,OLED and other fields.In this paper,the cyclized mer-Ir-?ppy?₃derivative ligand?ppy=phenylpyridine?was designed and synthesized using the structural diversity and easy modification of Ir???complexes.The frame method—the dynamic covalent chemical reaction method,constructed multiple iridium-containing metal-organic cages,and further studied their photocatalytic capabilities.?1?Design and synthesis of cyclic metal ligand mer-Ir-CHO,by modifying three aldehyde groups on the surface and reacting with rigid diamine?trans-cyclohexanediamine?in toluene/acetonitrile mixed solution by Schiff The alkali condensation reaction controlledly synthesized a multinuclear Ir???-containing supermolecular structure with a unit cell volume as high as 12414.1959?³.After the Schiff base bond in the structure was reduced to an imine bond,the entire cage structure performed It has strong photophysical properties and is used in the photocatalytic oxidation of?-ketoester alpha hydroxylation with a conversion rate of up to76%.?2?The mononuclear iridium complex has an octahedral space configuration.The racemic Ir?ppy?₃ complex can be used to obtain?and?single chiral enantiomers by chiral chromatography,or optically cyclized Ir???can be successfully synthesized by introducing chiral auxiliary ligand amino acids complex.In this chapter,by introducing chiral auxiliary ligands,I successfully split mer-Ir-?ppy?₃ into a pair of?and?-mer-Ir-?ppy?₃ enantiomers,and constructed a single hand Metal-Organic cage,to study the effect of chiral cage on?-keto ester?hydroxylation reaction.