Three-dimensional nets from star-shaped hexakis(arylthio)triphenylene molecules and silver(l) salts

This article reports a number of functional 3D networks based on the coordination bonds between the silver(l) ion and polycyclic aromatic 2,3,6,7,10,11-hexakis(organylthio)triphenylene (HRTT) molecules. First, 2,3,6,7,10,11-hexakis-(phenylthio)triphenylene (HPhTT) chelates with AgBF ₄ (or AgTf, where Tf is triflate) in the presence of hexafluorobenzene to form a 3D network (composition, HPhTT·AgBF4; space group, I4), where each Ag(I) atom is bonded to three HPhTT molecules and acts as a three-connected node that interconnects the trigonal HPhTT ligands. In addition to the relatively rare 8 ²·10-a topology, the network features distinct channel-like domains that incorporate various solvent molecules (e.g., acetone and tetrahydrofuran). The solvent molecules can be evacuated to produce a stable and crystalline apohost network, in which the solvent-accessible fraction of the cell volume is calculated to be about 16%. Second, chelation of 2,3,6,7,10,11-hexakis(4-methoxyphenylthio)triphenylene (HMOPhTT) and AgSbF ₆ in a 1:1 ratio results in a 3D network featuring a similar 8 ²·10-a topology and Ag(I) coordination environment. However, the crystallographic symmetry (space group Cc) is lowered, and the feature of porosity is much less distinct. The 3D networks show strong room-temperature fluorescence bands with λ _F,max = 450 nm, due to the π-electron fragment of the triphenylene group. © 2006 American Chemical Society.