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Three-Dimensional Nets from Star-Shaped Hexakis(arylthio)triphenylene Molecules and Silver(I) Salts

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journal contribution
posted on 06.02.2006, 00:00 by Kunhao Li, Zhengtao Xu, Hanhui Xu, Patrick J. Carroll, James C. Fettinger
This article reports a number of functional 3D networks based on the coordination bonds between the silver(I) 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 AgBF4 (or AgTf, where Tf is triflate) in the presence of hexafluorobenzene to form a 3D network (composition, HPhTT·AgBF4; space group, I4̄), 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 82·10-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 AgSbF6 in a 1:1 ratio results in a 3D network featuring a similar 82·10-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 λF,max = 450 nm, due to the π-electron fragment of the triphenylene group.