A comparison of the IS values obtained for Cu24(BDC-t Bu)24(L2)6 with different L2 ligands (Fig. ) highlights the ability of L2 to switch on and tune the electronic communication between MOP cages. The conversion of Cu24(BDC-t Bu)24 to Cu24(BDC-t Bu)24(bipy)6 via insertion of bipy ligands increased the distance between Cu2 PWs in adjacent MOP cages from 7.8 Å to 11.3 Å 20 (Supplementary Figs. and). Nonetheless, effective interactions between Cu2 PWs in adjacent MOP cages was enabled through electronic communication via the L2 π-framework, which lead to an increase from IS = 43 (2) for the MOP to IS = 73(2) for the MOF. Insertion of a longer linker, such as 4,4'-azopyridine lead to a smaller increase in IS value (54(2)). Notably, for L2 = dabco, which does not offer a π-framework for electronic communication, the IS value remained identical to that of the MOP, despite a contraction of the distance between Cu2 PWs in adjacent MOP cages from 7.8 Å to 7.0 Å upon dabco insertion (Supplementary Fig. ).