The structure-directing role of the inorganic secondary building unit (SBU) is key for determining the topology of metal organic frameworks (MOFs). Here we show that organic building units relying on strong Ir interactions that are energetically competitive with the formation of common inorganic SBUs can also play a role in defining the topology. We demonstrate the importance of the organic SBU in the formation of Mg2H6(H3O)(TTFTB)(3) (MIT-25), a mesoporous MOF with the new ssp topology. A delocalized electronic hole is critical in the stabilization of the TTF triad organic SBUs and exemplifies a design principle for future MOF synthesis.