Topological Engineering From Non‐Emissive Chiral Metallomacrocycle to Interlocked Architecture for Strong Circularly Polarized Luminescence

ABSTRACT Interlocked architectures are crucial for stabilizing specific conformations to achieve superior performance. Herein, we proposes a vacant π‐site recombination strategy to achieve significant luminescence enhancement through topological engineering from non‐emissive chiral metallomacrocycles ( R / S ‐Au 4 ) to highly circularly polarized luminescence (CPL) catenanes ( R / S ‐Au 8 ). The dynamical structural transformation of metallomacrocycles ( R / S ‐Au 4 ) to catenanes ( R / S ‐Au 8 ) was monitored by 1 H and 31 P NMR spectroscopy. Excited state dynamics and theoretical studies revealed that the increase of heavy atom effect in catenanes ( R / S ‐Au 8 ) effectively increases spin‐orbit coupling constant from 4.03 ( R ‐Au 4 ) to 48.22 cm −1 ( R ‐Au 8 ), facilitating the intersystem crossing between S 1 and T 1 . While R / S ‐Au 4 with flexible metallocyclic structures tend to rapidly relax the excited states through thermally vibrational processes, interlocked structures of R / S ‐Au 8 lead to better rigidity, thus effectively suppressing non‐radiative deactivation and facilitating radiative T 1 →S 0 relaxation, thus achieving highly efficient CPL with ca. 39% quantum yield in solution. Solution‐processed circularly polarized organic light‐emitting diodes (CP‐OLEDs) based on R / S ‐Au 8 attain high‐efficiency deep‐red circularly polarized electroluminescence (CPEL) peaked at 685 nm, with external quantum efficiency (EQE) of 9.9% and electroluminescence asymmetric factor of ± 2.2 × 10 −3 . In any case, this upgrading approach from discrete macrocycles to interlocked architectures opens a new avenue for developing high‐performance emitting materials and devices.