Synthesis And Properties Of Functional Metal-organic Coordination Polymers Guided By Catalysis

Metal-organic coordination polymers was widely used in heterogeneous catalytic because of their novel structures and unique properties.In this text,we synthesized heterogeneous catalysts based on metal-organic coordination polymers in the way of in-situ assembling,encapsulating active guest molecule and post-modification respectively,and severally study the nature of multifunctional catalysis,catalyzing tandem reaction and synergetic catalysis of them.I.We screened out two Cu(I)-based coordination polymers from our group previous works.Compound 1 is 1D zigzag structure,there was weak Cu···Cu force between the two Cu centers,[Cu Br2]-as external counter anion,attached to the 1D chain backbone.Compound 2 is 1D trapezoidal structure,in which [Cu2Br4]2– as counter ions are located between chains and bridge two neighbouring 1D single chains.We used these two compounds as heterogeneous catalysts to catalyze phenol acetylation and A3-coupling(aldehyde-alkyne-amine)reactions respectively.We found that 1 can highly catalyze these two reactions and the catalytic efficiency of 1 is more betrer than 2.Demonstrated that the bare [Cu Br2]-in 1 as active catalytic center that can minish steric hindrance of the reactions,so that the reactions can be fully carried out.II.We take advantage of a known structure of 3D Cu4I4-MOF,which can reversible absorb iodine to obtain a porous composite material of 0.75I2@Cu4I4-MOF,which not only can highly catalyze acetal deprotection and Friedel-Crafts alkylation of aldehyde with indole,but can promote the Friedel-Crafts alkylation reaction of acetal and indole with high yield.The catalysts can be reused five times with catalytic activity no significant loss,and the morphology of which was well preserved.It's the first time to utilize non-metal@MOF to highly catalyze an organic tandem reaction.III.We introduced thiourea group to Ui O-66-NH2 in the way of post-modification,conversion is 38.4%,the obtained compound Ui O-66-thiourea was characterized by IR,ESI-MS and PXRD and so on,and Ui O-66-thiourea was used to catalyzed silylcyanation of aromatic aldehydes,conversions all higher than 95%,the catalysts can reused at least five times with no significant conversion loss,realizing synergetic catalysis between MOFs and organic molecule.The study shows that metal-organic coordination polymers obtained by the way of in-situassembling,incorporating active guest molecule and post-modification all can cayalyze oaganic reactions with high efficiency,that enriched the kinds of catalysts and provided new methods to synthesis newly highly-efficient catalysts.