Kinetically Controlled Seeded Living Supramolecular Polymerization of Tb(III) Complex

ABSTRACT We describe the synthesis of metallosupramolecular polymers using a Tb 3+ complex as a primary building block. This synthesis is facilitated through the strategic manipulation of non‐equilibrium self‐assemblies, employing a living supramolecular polymerization method. Our extensive investigation into the metallosupramolecular polymerizations, which are both thermodynamically and kinetically regulated and centered around the Tb 3+ complex with bisterpyridine‐modified ligand ( R ‐L 1 ) incorporating R ‐alanine units, revealed noteworthy properties. These complexes initially form kinetically metastable aggregates, characterized by a coordination number of nine. This structure involves one Tb 3+ cation and three NO 3 − anions at one terpyridine moiety, while the opposite terpyridine moiety remains unoccupied. Intriguingly, these aggregates can transition into a thermodynamically more stable state, also characterized by a nine‐coordination number. In this state, each of the two terpyridine units is coordinated with one Tb 3+ cation and three NO 3 − anions, respectively. This transformative process is expedited by seed‐induced living polymerization. Therefore, we have successfully executed the seeded living supramolecular polymerization of the monomeric building unit under kinetically controlled conditions. This process yielded a metallosupramolecular polymer with a precisely regulated length and minimal polydispersity, demonstrating the potential of this approach in the design of advanced functional materials.