Molecular Design And Synthesis Of A Novel Kind Of Polycyclic (Aryil Ehter Ketone)S With Single-Crystal X-Ray Studyies

Since macrocyclic aromatic ether-ketones and ether-sulfones were first reported in the late 1980's, many kinds of aromatic macrocycles have been explored and studied as precursors of high-performance thermoplastics both theoretically and experimentally. However, beyond the ring-chain interconversion between macrocyclic aromatic ethers and linear, high molar-mass polymers, little attention is paid to the rigid macrocyclic structure and the nano-scale cavity of these macrocycles.Until these two years with the emergence of a new field of nano-technology called molecular architecture, the rigid aromatic macrocycles have began to gain more and more attention as a kind of nano-structural material because of their inherent advantages (a rigid cyclic structure, a rigid nano-scale cavity, good solubility, excellent resistibility for different chemical or physical conditions, etc). Especially compared with the other organic macrocycles such as crown ether, or, the rigid nano-scale cyclic structure is full of potential application in nano technology, such as acting as aromaticguest molecules or being ordered organized as a template for the growth of nanoparticles in a ordered way with chemical or physical methods.In this paper, we designed and synthesized a series of novle aromatic macrocyclic oligomers with one or two p-chlorophenyl substituents. Then with a nickel catalyzed coupling reaction, a novle kind of polycyclic(aryl ether ketone)s oligomer was obtained. All the structures are supported by MALDI-TOF MASS spectrum, and 1H NMR spectrum analysis.Five kinds of single crystal of the aromatic macrocycles synthesized were grown in different solvents. With the single-crystal X-ray studies, the nanoscale rigid cavity of the aromatic macrocycle was approved, and nature of the heteromorphism of aromatic macrocyclic oligomer was also explained with the study of two kinds of single crystal with different steric structures. The most interesting thing is that the space group of a non-chiral macrocycle was a chiral symmetry one.With a p-chlorophenyl substituent, the structure of the aromatice macrocyclic oligomer was unsymmetrical. Thedisymmetrical structure gives the macrocycle a much lower melt point and excellent melt flow index. So this kind of aromatice macrocyclic oligomer can be used as matrix in forming carbon fiber reinforced thermoplastic composites.