Metal-Templated Dynamic Reorganization of Macrocyclic Gold Complexes Toward an N-Doped Cycloparaphenylene Catenane

Self-assembly based on a single dynamic bond smoothly converges on its thermodynamic product, but this does not extend to an interlocked architecture composed of strained, fully π-conjugated rings such as [n]cycloparaphenylenes ([n]CPPs), because assembling such an architecture requires forming the interlocked topology and reorganizing the rigid backbone at the same time. Herein, we report that two dynamic processes designed to operate orthogonally, reversible Au(I)─C σ-bond exchange and exchangeable Cu(I)─N coordination, can be coupled to promote metal-templated dynamic reorganization. This process leads to the formation of an interlocked metal-complex precursor, which reductive elimination then converts into a [2]catenane composed of two mechanically interlocked, fully π-conjugated, nitrogen-doped [12]CPP-based nanohoops. Computational analyses provide insight into possible Cu(I)-templated intermediates involved in the formation of the interlocked structure. The embedded sp² nitrogen atoms further provide coordination sites for guest-dependent biasing of the co-conformational mechanical helical chirality. This work establishes dynamic metal-templated reorganization as a strategy for constructing strained, topologically complex π-conjugated architectures beyond the reach of conventional single-interaction self-assembly.