The Synthesis And Property Study Of Heteroatom Doped Sumanene

Buckybowls are interesting bowl-shaped polycyclic aromatic hydrocarbons resembling the fragments of fullerenes,which have attracted tremendous attention not only for their characteristic “open” curved structures,but also for their unique physicochemical properties.Sumanene is a C3v-symmetric buckybowl,which represents a basic unit of C60.The last decade has witnessed growing interests in sumanene chemistry including its coordination chemistry,asymmetric synthesis,materials science and its use as building blocks for the synthesis of large buckybowls.The properties of organic functional materials can be effectively tuned by heteroatom doping.In this dissertation,we focuse on the design and synthesis of heterosumanenes,and their structure and property changes as a result of the heteroatom doping will also be investigated.In the first part,we achieved an efficient two-step synthesis of iodine-doped sumanene for the first time from triphenylene-1,5,9-triamine,which can be prepared in decagram scale.The iodine-doped sumanene could be converted to pristine trithiasumanene,triselenasumanene and trisilasumanene under non-pyrolytic conditions,which posed considerable synthetic challenges.The products have been characterized by NMR,Mass spectra.Furthermore,trithiasumanene was proven to adopt a bowl-shaped geometry while trisilasumanene was planar by single crystal X-ray diffraction.This work enriches the sumanene chemistry and would inspire the study of iodine-doped to aromatic frameworks for the synthesis of novel curved and planar materials such as buckybowls and nanographenes.In the second part,a three-step synthesis of trisilasumanene and trigermasumanene was achieved using a threefold rhodium-catalyzed cyclodehydrogenation of Si/Ge-H and C-H bonds as the key step from triphenylene-1,5,9-triamine.Trigermasumanene was proven to adopt a planar geometry by single crystal X-ray diffraction for the first time.Investigation of their optical and electronic properties revealed that the LUMOs of sumanene were significantly stabilized by the doping of silicon and germanium atoms.The prepared trisilasumanene and trigermasumanene could be used as materials as well as the precusors for the synthesis of organic materials and nanographenes.