Mesolamellar phases containing [Re₆Q₈(CN) ₆]^4- (Q = Te, Se, S) cluster anions

We synthesized new mesostructured materials through the surfactant-templated assembly of octahedral rhenium cluster [Re ₆Q₈(CN)₆]^4- (Q = Te, Se and S) anions. The mesostructured lamellar phases with the general formula [C _nH_2n+1N-(CH₃)₃]₄[Re ₆Q₈(CN)₆] (n = 14, 16, 18; Q = Te, Se, S; 1: n = 14, Q = Te; 2: n = 16, Q = Te; 3: n = 18, Q = Te; 4: n = 16, Q = Se; 5: n = 16, Q = S) were prepared by an ion exchange/precipitation reaction of alkyltrimethylammonium surfactants and the corresponding cluster K ₄[Re₆Q₈(CN)₆] in an H ₂O/acetone medium at room temperature. The orange plate-like crystals of 1 and 4 were obtained by slow concentration of their solutions and their crystal structures determined by single-crystal X-ray diffraction. In the structure, the rhenium clusters form layers with a pseudo-hexagonal arrangement, and these inorganic layers are separated by a bilayer of interdigitated surfactant cations. Compounds 1-5 were characterized using powder X-ray diffraction, TEM, IR, Raman, FL, UV/Vis spectroscopy, and thermogravimetric analysis.