Tetrabromoalkylthiacalix[4]arenes（1a and 1b） reacted with excess bis（tetraethylammonium）-bis（1,3- dithiole-2-thione-4,5-dithiol）zincate（2） to give thiacalix[4]arene-thiones（3a and 3b） in the presence of Na2S. Two novel bistetrathiafulvalene-attached thiacalix[4]arene assemblies（5a and 5b） formed via triethyl phosphite-mediated cross-coupling of thiacalix[4]arene-thiones（3a and 3b） and 4,5-biscyanoethylthio-1,3-dithiole-2-one（4）. All the four new compounds were characterized by 1H NMR, 13C NMR, IR, MS spectra and elemental analysis. Meanwhile, the structures of thiacalix[4]arene-thiones（3a and 3b） were identified by X-ray analysis. In addition, the cyclic voltammograms of the resulting thiacalix[4]arenes containing electroactive TTF units（5a and 5b） were provided.
Two novel （thia）calixarene-based exTTF derivatives（3a and 3b） were prepared by Mitsunobu reactions in toluene using diethyl azodicarboxylate（DEAD） and triphenylphosphine（PPh3） system. The cyclic voltammograms of compounds 3a and 3b were provided, and two electron-irreversible waves with redox potentials were observed. Meanwhile, the intermolecular electron transfer（ET） properties of both compounds 3a and 3b towards p-chloranil（Q） and C60 were investigated via UV-Vis and fluorescent spectroscopies, respectively. The results indicated that the in- troduced nonoxidable metal ions（Al^3＋, Pb^2＋, Sc^3＋） might promote the intermolecular ET from compounds 3a and 3b towards Q ensembles, whereas the effects of Sc^3＋ were the most impressive. Furthermore, the effects of the same metal ions（Al^3＋, Pb^2＋, Sc^3＋） added for compound 3b were greater than those for compound 3a. Additionally, the pho- toinduced intermolecular ET from compounds 3a and 3b towards C60 was observed.
