Two thallium aryloxide compounds TIOC6F5 (TIOArF) and bis-3,5-TIOC6H3(CF3)(2) (TIOAr') have been recrystallized from THF and crystallographically characterized in different isomeric forms. The latter compound forms a solvated tetrameric cubane, {TlOAr'}(4)(THF)-T-., 1. The TIOArF compound crystallized with a similar stoichiometry, {TlOArF} 4, 2 THF, 2, but contains a {TI2(mu(2)-OArF)(4)} unit that includes a thallophilic interaction at a distance of 3.5943(15) angstrom. Solution (TI)-T-205 and (TI)-T-203 NMR studies of 1 and 2 support the retention of a cubane structure for 1 in solution and suggest a similar structure for 2 with coupled thallium centers down to -90 degrees C. Fluorescence spectroscopy data for both compounds 1 and 2 in THF are consistent with LMCT. DFT calculations of 1, 2, and three models of the {TI2(mu(2)-OArF)(4)} unit show a bonding overlap of the bridged thallium atoms in 2 and are also used to describe the bonding in 1. The structures of two heterobimetallic compounds, TI2Cu(OArF)(4), 4, and TI2Cu(OAr')(4), 5, with the {TI2(mu(2)-OArF)(4)} structural motif and thallophilic contacts of 3.86( 6) and 3.564(1) angstrom, respectively, are described. The crystal structures of the unsolvated of TlOArF, 2b, solvated heterobimetallic derivative TI2Cu(OAr')(4)center dot 2THF, 5b, and the monomeric (18-crown-6) TIOArF, 3, and (TI)-T-205 NMR spectra of TIOC6H5, 6, are also reported for comparison purposes.