Syntheses And Properties Of Macrocyclic Compounds Containing Tetrathiafulvalene Units

Tetrathiafulvalene(TTF) is able to exist in three different stable redox states(TTF, TTF⁺, and TTF²⁺). For this reason TTF derivatives have found widespread use in novel materials chemistry and supramolecular chemistry, for example, crown-annelated ligands, Langmuir- Blodgett film deposition, cation sensors, nonlinear optical materials, supramolecular switches, organic ferromagnets, and so on. During the last decades, the utility of TTF derivatives as building blocks in macrocycles, cyclophanes and cage structures has made TTF one of the most extensively studied molecules.In this thesis, the new concepts and developments in macrocyclic TTF chemistry were introduced firstly. The purpose of this contents is not to duplicate those aspects previously reviewed in the different fields but to give an overview of recently synthesized TTF-containing macrocyclic systems and to summarize their new applications.Secondly, the synthesis of three novel macrocyclic dimmer compounds were described by using two bis(pyrrolo)-TTFs based building block. Bis(pyrrolo)-TTF was prepared by a simple, non-classical pyrrole-constructed procedure. Alkyl and polyglycol chains were chosen as the linked groups between the two TTFs moieties, providing flexibility and adjusting the cavity size of the compounds. The target compounds were characterized by MALDI-TOF-MS spectra and will make it possibleFinally, we have directly combined porphyrazine chemistry with TTF chemistry and successfully prepared the first examples of single molecules, in which the intriguing optical and metal ion binding abilities of the porphyrazine ring system have been intimately coupled to the favorable redox properties of the TTF units. The symmetrical TTF-porphyrazine derivatives were characterized by *H NMR, IR and MALDI-TOF-MS. Q-bands characteristic of porphyrazine cores were observed in the UV/visible spectroscopy. Electron paramagnetic resonance (EPR) spectroscopy of Mg-tetrakis(TTF)-porphyrazine (15a, in Chapter 3) revealed a strong radical signal, as a broad singlet at g=2.0059. Quantitative EPR measurements showed that product 15a contained 3% unpaired spin, indicating that compound 15a consisted of a mixture of the neutral porphyrazine and the radical cation porphyrazine. The presence of radicals rendered completely isolation and accurate photophysical charaterization of the compound 15a almost impossible. To elucidate the effect of annulation of a TTF unit directly onto the porphyrazine ring system further, we have prepared the asymmetric mono(TTF)-porphyrazines characterized by MALDI-TOF-MS. The appearance of a red shifted maximum absorption in the UV/visible spectroscopy. This work paved the way for the study of other systems with porphyrazine core and TTF units, which combine the versatile electrochemical, optical, and coordination properties of porphyrazine with the redox properties of many TTF units.