Crown Ether Vinylogous Tetrathiafulvalene Receptors:  Complexation Interference on the Molecular Movements Triggered by Electron Transfer

Abstract

The synthesis of a series of crown ether substituted vinylogous tetrathiafulvalenes (TTFVs) has been carried out through oxidative coupling of bisdithiafulvenes. These new receptors have been fully characterized using electrochemical, spectroelectrochemical, and molecular modeling experiments. These studies show that, upon oxidation, either a clip movement (TTFVs 3a,b) or a stretch movement (TTFV 3c) occurs, depending on the length of the crown ether chains. Preliminary electrochemical studies, undertaken on TTFV 3c in dichloromethane, show a little shift of the first standard oxidation potential toward more positive values upon addition of the Pb(2+) ion, but a considerable variation of the electron-transfer kinetics. This result introduces an interesting concept for the preparation of sensors not based on thermodynamic variations but on kinetic modifications of the electron transfer.

Bisquinolones as chiral fluorophores – A combined experimental and computational study of absorption and emission characteristics

“…In recent years, such crown ethers have attracted much attention for their interesting binding properties with metal and organic cations [17,18]. In general, crown ether macrocycles with circular cavities have been widely studied [19] with respect to their complexation of predominantly alkali and alkaline earth metals and ammonium salts [20].…”

Bis[2-(1,3-benzothiazol-2-ylsulfanyl)ethyl] ether

“…For coordination polymers in supramolecular chemistry and crystal engineering, see: Robinson & Zaworotko (1995); Yaghi & Li (1996); Fujita et al (1995); Tong et al (2000); Bu et al (2003); Long et al (2004); Massue et al (2007); Zou et al (2004). Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al, 2009).…”

“…Bis(2-chloroethyl)ether (0.02 mol, 2.86 g) was added dropwise to a hot mixture solution (353 K) of 2-mercaptobenzothiazole (0.04 mol, 6.69 g), KOH (0.04 mol, 2.24 g) in ethanol (100 ml), and the mixture was further stirred at 353 K for 15 h. After cooling, the precipitate was filtered, washed with ethanol and water, and recrystallized from ethanol to obtain white powder. Yield: 56% (Bu et al, 2003;Massue et al, 2007;Long et al, 2004). 1 H NMR (CDCl 3 , 400 MHz): 3.56 (t, 4H), 3.89 (t, 4H), 7.25 (m, 2H), 7.39 (m, 2H), 7.70 (d, 2H), 7.82 (t, 2H).…”

Intramolecular alkyne–dithiolium cycloaddition: a joint experimental and DFT mechanistic study

“…1,4-Dithiafulvenes (DTFs) because of their excellent electrondonating properties [1][2][3][4] have been increasingly employed over the past years as active components in organic optoelectronic materials and devices such as chemical sensors, [5][6][7][8][9][10][11] molecular switches, [12][13][14][15] non-linear optic-phores, 16 photovoltaic cells, [17][18][19][20][21][22][23] eld-effect transistors (FETs), [24][25][26] and so forth. Besides acting as p-electron donors, DTFs also provide synthetic access to another intriguing class of tetrathiafulvalene (TTF) analogues, namely tetrathiafulvalene vinylogues (TTFVs), through a straightforward oxidative dimerization reaction.…”