Synthesis And Properties Of Tetrathiafulvalene Derivatives

Tetrathiafulvalene(TTF) is able to exist in three different stable redox states(TTF, ITF⁺ , 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, TTF and TTF derivatives have been utilized as building blocks in macrocycles, cyclophanes and cage structures, which is one of the most extensively studied fields.In this paper, first, we synthesized four the tripod-type compounds with three TTF unit as electronic donor in good yields by Cyanothylthio-3,6,7-trisubstituted TTF reacting with tri(2-iodoethyl)amine or tribromomethylbenzene. Their structures were confirmed by ¹H NMR, ¹³C NMR and elemental analysis and their electrochemical behaviors were investigated by meanes of cyclic voltammetry. According to UV and ¹H NMR, target compounds didn't include C₆₀ in solution. Compound 4c exhibited the unique redox processes on account of its p-electron rigid structure.Secondly, we successfully obtained four monopyrrolo-tetrathiafulvalene-p-A (MPTTF-p-A) type compounds and two monopyrrolo-tetrathiafulvalene-p-D' (MPTTF-p-D') type compounds from formylated precursor. The target compounds were characterized by ¹H NMR, ¹³C NMR, MALDI-TOF-MS. From UV-Vis spectra of target compounds 20a-b, the intramolecular charge-transfer (CT) absorption bands are observed. Compounds 17a-b and 20a-b likely have good third-order NLO properties due to having conjugated pull-push structural unit. Finally, the synthesis of...