Highlighting the utility of TEMPO-polyCAT as a heterogeneous system, the material was cycled through 9 rounds of the above reaction with 3 × 30 min washes between each cycle. 1 H NMR conversion of 1 to 2 was >95% for the first 5 cycles and decreased during cycles 6-9 (Fig. ). While TEMPO-polyCAT maintained its gel form throughout this process, it became grey in color after 9 reaction cycles, perhaps indicating decomposition of TEMPO. Nevertheless, this performance over 9 cycles amounts to nearly an order-of-magnitude increase in the catalyst turnover number (TON). Finally, to demonstrate the long-term storability of TEMPO-polyCAT, a sample was fabricated, dried under a stream of nitrogen for 30 min, and stored at -20° C for 3 weeks. After this time, the material was swelled in CDCl3 and used to catalyze the oxidation of 1; no loss in activity was observed (>95% NMR conversion, Fig. ). Au-PolyCATs for Au(I)-catalyzed cyclization reactions. Reek and coworkers have reported fascinating homogeneous bis-pyridyl-based Au(I) phosphine complexes (e.g., Au-CL, Fig. ) that are poor catalysts themselves but, due to local concentration effects, function as highly active catalysts when assembled into MOCs through Pd(II) coordination. Successful translation of these systems to polyCATs would not only further the polyCAT concept but would provide further evidence for the presence of assembled catalytic MOC junctions within polyCAT networks. Thus, a new polyCAT-Au-polyCAT-was prepared following the same procedure used for TEMPO-polyCAT but by simply exchanging TEMPO-CL for Au-CL (here a modified C:P ratio of 16:8 instead of 20:4 was necessary due to the solubility of Au-CL). The SAXS curve for Au-polyCAT was very similar to that of TEMPO-polyCAT (Figure ),