Auto‐Click Synthesis of a Copper(I) –N ‐Heterocyclic Carbene Porous Organic Polymer and Its Transmetalation to Palladium(II) for Azide–Alkyne Cycloaddition and Cross‐Coupling Reactions

We report herein the synthesis of a copper(I)– N ‐heterocyclic carbene (NHC) porous organic polymer (POP), Cu(I)‐NHC‐POP1 , obtained via an “auto‐click” strategy, where a preformed azide‐decorated Cu(I)–NHC complex acts simultaneously as catalyst and building block for the assembly of the porous framework. Further post‐synthetic transmetalation of Cu(I) to Pd(II) afforded Pd(II)‐NHC‐POP1 , enabling access to two distinct catalysts from the same NHC scaffold. The materials were characterized by Fourier‐transform infrared spectroscopy, powder X‐ray diffraction, scanning electron microscopy with energy‐dispersive X‐ray spectroscopy, thermogravimetric analysis, N 2 adsorption−desorption isotherms, and X‐ray photoelectron spectroscopy. Catalytic tests indicated that Cu(I)‐NHC‐POP1 promotes copper‐catalyzed azide–alkyne cycloaddition with high conversion, under air conditions, and catalyzes Ullmann‐type C–N and C–O couplings. Following transmetalation, Pd(II)‐NHC‐POP1 was found to be active in Suzuki‐Miyaura cross‐coupling, achieving excellent conversions with aryl iodides and moderate activity with aryl bromides. Although metal leaching limits recyclability under the tested conditions, the NHC‐based polymer can be remetalated or transmetalated to restore metal content and switch catalytic function. These results highlight the material as a reconfigurable metal–NHC polymer platform.