Hexakis(4-(4-carboxylphenyl)phenyl)benzene, H6cbb, was used to prepare the rod-based metal–organic frameworks (rod-MOFs) [Mn4(cbb)(dmf)2(OAc)2] CTH-50 and [Gd3(cbb)(dmf)2(H2O)(OAc)3] CTH-51 by solvothermal synthesis (dmf = N,N-dimethylformamide) with single crystal diffraction revealing that CTH-50 (by X-ray) and CTH-51 (by electron diffraction) can be described as 5- and 6-connected yav-nets. Gas sorption analysis gave a BET surface area of 787 m2/g for CTH-50 and 187 m2/g for CTH-51, with CTH-50 having an Ideal Adsorbed Solution Theory (IAST) selectivity for SF6 of 35 at 10 kPa, and thermogravimetry indicated the possible stability of CTH-50 to 300 °C and CTH-51 to 400 °C.