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 I 2 Cl 2 (H 4 TC4A)](CH 3 OH) ( 1 ) and [Cu I 2 Cl 2 (H 4 PTC4A)](CH 3 OH)(CHCl 3 ) 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 CH 3 OH/CHCl 3 (1:1) solvent and reassembled in air at room temperature to two other structures, [Cu II 4 Cl 3 (HCO 2 )(TC4A)(CH 3 OH) 2 (H 2 O)](CHCl 3 )(CH 3 OH) 2.7 ( 3 ) and [Cu II 4 Cl 4 (PTC4A)(CH 3 OH) 4 ] ( 4 ), respectively. All these four compounds were characterized by TG analyses, FTIR spectroscopy, and single‐crystal X‐ray diffraction analyses. Compounds 1 and 2 feature two‐dimensional layered networks, while compounds 3 and 4 are assembled by some tetranuclear units. The luminescence of compounds 1 and 2 in the solid state and magnetic properties of compound 3 were studied.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)