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

Abstract

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.