American Chemical Society
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Synthesis, Conformation, and Complexation of Novel 25,26,27,28- Tetrahydroxy-5,11:17,23-bis[[2,2‘-thioxydi(o-phenylene)dithioxy]- diphenylthio]calix[4]arene

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journal contribution
posted on 2005-01-21, 00:00 authored by Kyongho Yoon, Kyongtae Kim
Calix[4]arenes 1a,b having an electron-donating group, i.e., OH and OMe, at the lower rim reacted with thianthrene cation radical perchlorate in CH3CN at room temperature to give the corresponding thianthrenium perchlorates 3a,b in excellent yields. Treatment of 3a,b comprising a mixture of conformational isomers with NaSH·xH2O in DMF at reflux afforded the sulfur-containing cyclized compounds 4a,b, respectively. Compound 4a having a cone conformation consisted of two conformational isomers in a ratio of 0.077:1. Temperature-dependent 1H NMR study in DMF showed that conformational isomerization between the two isomers occurred with energy barriers of 14.97 and 14.10 kcal/mol at 100 and 110 °C, respectively. The Jobs plot of 4a against Ag+ picrate indicated that compound 4a strongly produced a 1:2 complex with Ag+ ions. Molecular mechanics calculations indicated that the conformation of the energy-minimized 4a−2Ag+ picrate complex had two crushed pyramidal geometries made up of Ag+ ion and four sulfur atoms, i.e., S1, S2, S4, S5 and S6, S7, S9, S10, respectively.