Self-Assembly from Two-Dimensional Layered Networks to Tetranuclear Structures: Syntheses, Structures, and Properties of Four Copper-Thiacalix[4]arene Compounds

Two new copper-thiacalix[4]arene compounds, [Cu-2(1)-Cl-2(H(4)TC4A)](CH3OH) (1) and [Cu(I)2Cl(2)(H(4)PTC4A)](CH3OH)(CHCl3)(0.5) (2) (where H(4)TC4A = p-tert-butylthiacalix[4]arene and H(4)PTC4A = p-phenylthiacalix[4]arene), were synthesized by the solvothermal method in the mixed CH3OH/CHCl3 (1: 1) solvent and reassembled in air at room temperature to two other structures, [(Cu4Cl3)-Cl-II(HCO2)(TC4A)(CH3-OH)(2)(H2O)](CHCl3)(CH3OH)(2.7) (3) and [(Cu4Cl4)-Cl-II(PTC4A)(CH3OH)(4)] (4), respectively. All these four compounds were characterized by TG analyses, FTIR spectroscopy, and singlecrystal X-ray diffraction analyses. Compounds 1 and 2 feature two-dimensional layered networks, while compounds 3 and 4 are assembled by some tetranuclear units.