Construction And Performance Evaluation Of Photoactive Ir-Cu-Based Metal-Organic Frameworks

Photoactive metal-organic frameworks(MOFs)have become one of the research hotspots in materials science due to their promising applications in photocatalysis and molecular recognition.The key issue includes how to precisely arrangement of the components in the crystalline material to realize the synergy and coupling between their multifunctional properties,and at the same time,in a controllable manner to fabricate the frameworks by reasonal selection and assembling of the building blocks.In this thesis,homochiral cationic transition metal Ir(Ⅲ)complexes with excellent photophysical and chemical properties was designed and synthesized as the building blocks,and the assembly processes with Cu~+to construct photoactive MOFs were studied.Furthermore,the photocatalytic properties of selected materials were also explored.(1)The homochiral cyclometallized Ir(Ⅲ)ligand Ir-bpy containing two pyridine N coordination sites was designed and synthesized.Further assembly with Cu~+,we obtained two cases of homochiral,photoactive metal-organic framework materialsΛ-Ir-Cu-MOF1 andΔ-Ir-Cu-MOF1.Coupled photocatalysis and transition metal ion coordination catalysis under visiblelightconditions,theC-Ccouplingreactionbetween N-phenyl-1,2,3,4-tetrahydroisoquinoline and phenylacetylene derivatives was achieved,which showed good reaction efficiency and stereoselectivity.(2)By expanding the above Ir(Ⅲ)ligand,another building block(Ir-qpy)containing four pyridine N coordination sites was designed and synthesized.The coordination assembly of Ir-qpy with Cu~+leaded to the formation of a novel photoactive metal-organic frameworks Ir-Cu-MOF2.The crystal structure of Ir-Cu-MOF2 has a double interpenetrating topology,in which Cu~+is coordinated with four‘N’from four Ir(Ⅲ)complex building blocks.Ir-Cu-MOF2 also presents phosphorescent emission properties,which lays a foundation for its further application in photocatalysis research.