This result highlights the ability for host-guest binding to stabilize the metal-ligand coordination interaction through the unique nested configuration present in this system. Such behavior contrasts with the properties observed for previously reported supramolecular gels with multiple discrete interactions, where, upon incorporation of additional interaction types and strengths, the terminal relaxation mode is unaffected. . We hypothesized that guest inclusion could provide a means to stabilize polyMOC gels under conditions that are typically incompatible with network formation, such as in the presence of super-stoichiometric metal ions. Stoichiometry is critical for the formation of both traditional and supramolecular polymer networks, and previous studies have explored the impact of offstoichiometry components on metallogel properties. With sub stoichiometric metal, crosslinking density is proportional to metal ion concentration; when there is excess metal, incomplete, lower-functionality metal-ligand complexes form, precluding gelation. In our polyMOCs, addition of superstoichiometric Pd 2+ would therefore be expected to drive MOC disassembly and produce free ligands coordinated to two palladium ions (Figure ). To test the potential ability of guests to stabilize MOC structures under these conditions, assembly of MOC was attempted with 4 equiv of [Pd(MeCN)4][OTf]2. When using this super-stochiometric Pd 2+ , a mixture of products is obtained as supported by 1 H NMR (Figure , orange spectrum). The alternating addition of DAQ and Pd 2+ (Figure ). Both HSO4 and NO3 can induce a sol-gel transition in polyMOC gels in the presence of excess Pd 2+ , but in line with their lower binding affinities, the extent was less pronounced than for DAQ. A sol-gel phase diagram for assembly of polyMOC gels containing 1 equiv of each guest and between 1 and 5 equiv Pd 2+ was constructed (Figure ), showing that the amount of excess Pd 2+ that can be tolerated before gelation is precluded is proportional to guest binding strength. Materials with 4 equiv Pd 2+ underwent a solgel transition when 1 equiv of all guests were added, representing an unselective guest-sensing response. In contrast, systems with 4.