Studies" section of the Supporting Information for details). This difference in affinity for DAQ between MOC and N-MOC is sufficiently strong to drive considerable self-sorting to preferentially incorporate L1 into MOC structures when equimolar amounts of L1 and L2 (0.5 equiv in total) were mixed super-stoichiometrically with 0.375 equiv [Pd(MeCN)4][OTf]2 in DMSO (5 mM solution of Pd 2+ ). For this system, we first quantified the preferential incorporation of L1 into MOC structures upon guest addition using 1 H NMR spectroscopy, as Ha and Hb resonances for un-bound L1 and L2 could easily be resolved. All guests were observed to preferentially drive L1 incorporation into MOC structures with an extent proportional to the differential guest binding strength between MOC and N-MOC (Figure ). The greatest shift in ligand incorporation occurred in the presence of >1 equiv DAQ, resulting in a 12% increase in the fraction of L1 in MOC structures, which corresponds to a 50% increase in the selectivity for L1 incorporation over L2. Interestingly, when 3 equiv NO3 were added to the mixed ligand system containing 1 equiv DAQ, the ratio of free to cage-bound L2:L1 was quickly shifted (within 15 min at room temperature) from 2:1 to 1.5:1 (Figure ), illustrating the ability to reversibly modulate ligand self-sorting in situ through introduction of less-selective guests. Looking to translate this self-sorting effect into a polyMOC gel system, an optimized ratio of polymer-bound and small-molecule ligands was required. Using Macosko-Miller theory, we modeled the predicted network structures that could be formed through arbitrary combinations of PL, L2 , and Pd 2+ and derived gelation criteria based on the proportions of L2 : PL and of L2 + PL : Pd 2+ , and a self-sorting preference factor, denoted as 𝜌 !"#:%# , 𝜌 #:%& !" , and 𝜙, respectively.