Corannulene Derivatives: Design,Synthesis And Structure-Property Relationship

Corannulene,the smallest bowl-shaped molecule,has attracted a lot of attention owing to its unique properties and tailorable structure.The class of indenocorannulenes show photophysical and electrochemical properties different from corannulene depending on the degree of bowl depth and curvature.In this dissertation,the syntheses of three indenocorannulenes,three aza-indenocorannulenes,four thiophene fused indeocorannulenes,and three ladderane bridged corannulenes,as well as to their X-ray crystal structures,photophysical and electrochemical properties,are presented.In Chapter 1,we summarized the corannulene chemistry,from the first synthesis of corannulene to its kilogram-scale synthesis.We also summarized the synthesis of aza-corannulenes and thiophene fused corannulenes,chiral corannulenes and ladderane.In Chapter 2,the syntheses of three indenocorannulene structures,together with their X-ray crystal structures is presented.We show that derivatives of diindenocorannulene can be used as general building blocks for "designed" bowl-in-bowl supramolecular materials.In Chapter 3,the syntheses of three aza-indenocorannulenes,including two chiral compounds,is presented together with their resolution.The absolute configuration of the enantiomers of these two chiral compounds is determined by comparison of the experimental vibrational circular dichroism and electronic circular dichroism spectra with that of the quantum mechanically predicted spectra.In Chapter4,syntheses of four thiophene fused indenocorannulenes,including two chiral compounds is introduced.Optical resolution of these two chiral compounds as well as the bowl inversion/racemization energy are presented and discussed.The absolute configuration of the enantiomers of one chiral compound is discussed as determined by X-ray crystallography.In Chapter 5,the synthesis and X-ray crystal structure of a hybrid ladderane bridged dicorannulene is presented.With a length of ?3.1 nm,this compound also provides an opportunity to investigate the electron transfer between two corannulene moieties through cyclobutane bridge.In Chapter 6,we summarize and outlook our work,and highlight the innovations of this thesis.