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

Bryce, M.R.; Batsanov, A.S.; Finn, T.; Hansen, T.K.; Moore, A.J.; Howard, J.A.K.; Kamenjicki, M.; Lednev, I.K.; Asher, S.A.

Abstract

The synthesis of O4S2-crown annelated derivatives of 9,10- bis(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, two-electron 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 (< 30 mV) were observed for complexation of Li+, K+ and Ba2+. UV/Vis spectrophotometric studies of metal binding (Na+ and Ag+) to 9 are consistent with the simultaneous formation of 1:1 and 1:2 complexes. The X-ray crystal structures of compounds 10 and 12CH2Cl2 are reported. The anthracenediylidene moiety of 12 is U-shaped due to the boat conformation of the central (quinodimethane) ring and folding of both 1,3-dithiole rings, providing an overall saddle conformation. The folding in 10 is reduced as steric crowding is relieved by removal of one of the 1,3-dithiole units.

Citation

Bryce, M., Batsanov, A., Finn, T., Hansen, T., Moore, A., Howard, J., Kamenjicki, M., Lednev, I., & Asher, S. (online). 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. European Journal of Organic Chemistry, 933-940

• Journal Article Type: Article
• Journal: European Journal of Organic Chemistry
• Print ISSN: 1434-193X
• Electronic ISSN: 1099-0690
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Issue: 5
• Pages: 933-940
• Public URL: https://durham-repository.worktribe.com/output/1556133
• Publisher URL: <Go to ISI>://000167272700009