Study On Cu(I)-catalyzed C-N And C-O Bond Formations And Their Applications In The Synthesis Of Cyclometalated Complexes

In this dissertation,we developed two kinds methods for synthesizing N-heteroarylcarbazole bromide derivatives and hydroxy-N-heteroarylcarbazole derivatives,which were applied to the synthesis of nonvel phosphorescent tetradentate cyclometalated Pt???/Pt???complexes.Subsequently,the synthetic method for the electron transport material of BPyTP-2 was optimized.1.A CuCl-catalyzed C_aryl-N cross-coupling reaction between carbazole derivatives and2-bromopyridine derivatives has been developed for the synthesis of heteroarylcarbazole derivatives employing N-methyl-imidazole and ^tBuOLi as ligand and base respectively,both of which were found to promote the reaction significantly.Low costs and low loading of both catalyst and ligand?1-2 mol%?,together with high reaction yields?up to 99%?rendered this practical reaction to be suitable for large-scale preparation,and could be useful in material science.2.An efficient and practical method for hydroxylation of N-heteroarylcarbazole bromide catalyzed by CuCl was developed.Compared with the reported routes,the reaction was with broad functional group and high yield?up to 98%?.Moreover,the catalysts,ligand and bases were cheap and easily synthesized.Furthermore,reaction steps were greatly shortened and operation was simple in the reaction.This approach was suitable for large-scale preparation,and was successfully applied in gram-scale synthesis of PtNON and PdNON phosphorescent emitters,demonstrating its practicability in material science.3.With N-heterocarylcarbazole as the cyclometalated auxiliary ligand,nine sky blue or yellow neutral Pt???phosphorescent complexes were designed,synthesized and characterized.The influence rules of heteroatoms located functional groups were summarized.These kinds of metal complexes were easy prepared,which had remarkable thermal stability?364-421 ^oC?,electrochemical stability and photophysical properties.Especially,the sky-blue phosphorescent complex containing triazole derivatives as function group could achieve up to 100%of quantum efficiency.4.With N-heterocarylcarbazole as the cyclometalated auxiliary ligand,20 neutral Pd???phosphorescent complexes were designed,synthesized and characterized.17 kinds of blue materials had been found,which had remarkable thermal stabilities?350-393 ^oC?,electrochemical stabilities and photophysical properties.At the same time,the stabilities and physical properties of cyclometalated Pd???metal complexes were discussed systematically.All complexes whose functional groups containing the pyrazole and triazole moieties exhibited improved properties.These results could further guide the synthesis of phosphorescent materials and make sense for the development of blue phosphorescent materials.5.An efficient and practical synthesis of 2,7-bis?4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl?-triphenylene from two cheap and available chemicals in five steps with a total yield of48.6%was developed.This process had been successfully applied in the synthesis of electron transport material?ETM?BPyTP-2 in the gram scale.Compared with the reported routes,low costs and simplicity of operator together with high reaction yields render this practical reaction to be suitable for large-scale preparation and could be useful in material science.