Polymer Networks with Cubic, Mixed Pd(II) and Pt(II) M 6 L 12 Metal-Organic Cage Junctions: Synthesis and Stress Relaxation Behavior.

Metal-organic cages/polyhedra (MOCs) are versatile building blocks for advanced polymer networks with properties that synergistically blend those of traditional polymers and crystalline frameworks. Nevertheless, constructing polyMOCs from very stable Pt(II)-based MOCs or mixtures of metal ions such as Pd(II) and Pt(II) has not, to our knowledge, been demonstrated, nor has exploration of how the dynamics of metal-ligand exchange at the MOC level may impact bulk polyMOC energy dissipation. Here, we introduce a new class of polymer metal-organic cage (polyMOC) gels featuring polyethylene glycol (PEG) strands of varied length cross-linked through bis-pyridyl-carbazole-based M ₆ L ₁₂ cubes, where M is Pd(II), Pt(II), or mixtures thereof. We show that, while polyMOCs with varied Pd(II) content have similar network structures, their average stress-relaxation rates are tunable over 3 orders of magnitude due to differences in Pd(II)- and Pt(II)-ligand exchange rates at the M ₆ L ₁₂ junction level. Moreover, mixed-metal polyMOCs display relaxation times indicative of intrajunction cooperative interactions, which stands in contrast to previous materials based on point metal junctions. Altogether, this work (1) introduces a novel MOC architecture for polyMOC design, (2) shows that polyMOCs can be prepared from mixtures of Pd(II)/Pt(II), and (3) demonstrates that polyMOCs display unique relaxation behavior due to their multivalent junctions, offering a strategy for controlling polyMOC properties independently of their polymer components.