Crown-Annelated 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene Derivatives as Cation Sensors: Synthesis, X-ray Crystal Structures, Voltammetric and Spectroscopic Monitoring of Metal Complexation

Abstract

The synthesis of O 4 S 2 -crown annelated derivatives of 9,10bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene using the novel Horner−Wadsworth−Emmons reagent 7 is reported. The bis-and mono-crown systems 9 and 12 function as efficient ligands in the voltammetric and UV/Vis spectroscopic recognition of Na + and Ag + . Solution electrochemical studies reveal that metal complexation to the crown unit(s) leads to a significant positive shift in the potential of the first, twoelectron oxidation wave of 9 and 12 [maximum shift E 1 ox = 115 mV for 9 in the presence of Ag + (ca. 10 molar equivalents)]. Considerably smaller shifts (Ͻ 30 mV) were observed [ ‡] Molecular Saddles, 5. Ϫ Part 4: N. Godbert, A.

Tetrathiafulvalene (TTF) derivatives: key building-blocks for switchable processes

“…One family is based on compound 17, 53 and related polyether derivatives described recently. 54 Three additional examples have appeared in the very recent literature, namely a crown ether vinylogous TTF receptor 18 55 whose cation binding ability is accompanied by a tuning of intramolecular movements (vide infra), and two extended TTF-based receptor 19 56 and 20 57 that contain, respectively, a furano-quinonoid or a thienylene spacer between the 1,3-dithiol-2-ylidene rings.…”

“…near the binding cavity. On the other hand, compound 17 involves an anthracenylbased extended-TTF unit (exTTF), 53,54 whose electrochemical behavior is clearly distinct from that of TTF; this species is oxidized following a single two-electron oxidation to generate the dication exTTF 2+ . A good affinity of 17 for Na + and Ag + could also be demonstrated, with a remarkable electrochemical response to metal complexation being observed.…”

Tetrathiafulvalene derivatives as cation sensor: density functional theory investigation of the hyper-Rayleigh scattering first hyperpolarizability

“…The techniques of detecting metal ions have attracted considerable attention because of their potential application in chemistry, clinical biochemistry, toxicology, and environmental science, etc. [1][2][3][4][5][6] In general, the detection of metal ions is mainly based on the linear optical response. By contrast, the nonlinear optical (NLO) response has rarely been considered for detecting metal ions, especially second-order NLO property.…”

Colorimetric and electrochemical Pb2+ detection by imine-bridged tetrathiafulvalene-pyridine derivatives

“…TTF supramolecular systems containing macrocyclic host unit capable of cation binding have attracted considerable attention because the complexation of the host with an ionic guest can induce a change in physico-chemical response (e.g. spectral or electrochemical) [16][17][18][19][20][21] . In general, upon metal ion-binding in TTF macrocyclic systems, the first oxidation potential (E 1 ox ) increases, while the second one (E 2 ox ) remains unchanged, which is rationalized by the expulsion of the cation after the first oxidation.…”