Study on Syntheses and Properties of Macrocyclic Commounds Having Electronic Active Tetrathiafulvalene Unit

【摘要】：For more than three decades tetrathiafulvalene (TTF) and its derivatives have been intensively studied on account of their unique π-electron-donor properties. Furthermore, there has recently been an increasing interest in incorporating TTF into molecular, macrocyclic, and supramolecular systems capable of acting as sensor , catalysts, or switches at the molecular level. The following three research activities of our interests are described:Crown ether annelated TTF systemSelf-coupling of 4,5-dithia crown ether-l,3-dithiole-2-thione derivativesofferded the symmetric bis-crown-ether TTF derivatives and cross-coupling with 4,5-dimethylthio-l,3-dithiole-2-one gave asymmetric mono crown-ether TTF derivatives in net triethyl phosphite. The electrochemical and ion-sensing properties of crown-ether TTF derivatives were studied by means of cyclic voltammetry.Oligomeric monomacrocycles including tetra-TTF units( e.g. tetramer)A general and efficient four-steps synthesis of nanoscale octathia 36-crown-12 annulated tetrathiafulvalene tetramer , starting from the 2,3-biscyanoethyl TTF building block is described, and the tetramer showed macrocyclic effect and the considerable charge-transfer interaction with [60] fullerene by means of cyclic voltammetry (CV) and ~1H NMR spectroscopy.Tetrathiafulvaleno-annelated fully conjugated porphyrazine systemIn addition, we prepared the first tetrathiafulvaleno-annelated fully conjugated porphyrazines which contain butylsulfanyl group or thiacrown ether pendants. Five tetrathiafulvaleno-annelated fully conjugated porphyrazine derivatives were characterized by *H NMR, IR, MALDI-TOF-MS, and UV/visible spectrometry, respectively.In summary, tetrathiafulvalene (TTF) is a molecule with unique electronic properties that challenges the creativity and inventiveness of chemists in areas such as organic chemistry, polymer and materials chemistry, and supramolecular chemistry. The knowledge obtained during its thirty years of existence paves the way for the development of the outstanding properties that TTF derivatives display. Thus, TTF faces the new century as one of the target molecules to be exploited in depth.