The temperature-dependent assembly of two 3-D CuI coordination polymers containing calix[4]-bis-thiacrown with different networking motifs are reported. Upon removal of the coordinated solvent molecules the initial solvent-coordinated polymer undergoes a unique single-crystal-to-single-crystal transformation to the desolvated polymer. Structural characteristics observed in the solvent-coordinated and the desolvated polymers also reveal related solvato-photolunimescence "off-on" behavior.

Temperature-Dependent 3-D CuI Coordination Polymers of Calix[4]-bis-dithiacrown: Crystal-to-Crystal Transformation and Photoluminescence Change on Coordinated Solvent Removal

Assembly reactions of mercury(II) halides (Cl, Br, and I) with two O2S2 macrocycles (L(1) and L(2)) having different interdonor (S...S) distances were investigated, and four types of supramolecular complexes (1-4b) were obtained depending on the S...S distances as well as the size of the halide anions. Photoluminescence of these compounds was also studied.

Ligand- and Anion-Directed Assembly of Exo-Coordinated Mercury(II) Halide Complexes with O2S2-Donor Macrocycles

Solvato-PL switching and shrinking-and-opening process: we present two CuI coordination polymers of calix[4]-bis-monothiacrown (L) obtained in the absence (1) and presence (2) of KI. The structures show not only very unusual CuI-based network arrangements but also unique reversible photolunimescence switching behavior induced by removal of coordinated solvent. Furthermore, upon inclusion of K+ ions the crown ring shrinks leading to “opening” of opposite aromatic rings in the host calixarene unit, rare behavior for this class of compound.

Ii Yoon

Papers

Calix[4]thiacrowns as Ditopic Hosts for Homo- and Heterobinuclear Accommodation: First Report of a Chopsticks-Type π-Coordination