Herein we report a variety of supramolecular architectures that are self-assembled by the highly charged anionic Ti4L6 (L = embonate) cages and noble-metal Ag+ ions in the presence of the different ligands, including six Ti4L6-Ag(PPh3) cages in whose structures the Ti4L6 cage catches various in situ formed [Ag(PPh3)](+) moieties by a coordination bond and one cocrystal superstructure of a Ti4L6 cage with an in situ generated [Ag-2(Ph2P(CH2)(5)PPh2)(3)](2+) cage via supramolecular interactions. In addition, the third-order nonlinear-optical properties of these compounds are investigated in detail.

GAS SORPTION; CONSTRUCTION; FLUORESCENCE; TETRAHEDRON; DISCRETE

Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences; GUILIN UNIVERSITY OF TECHNOLOGY