Dual Enhancement of Phosphorescence and Circularly Polarized Luminescence through Entropically Driven Self‐Assembly of a Platinum(II) Complex

Addressing the dual enhancement of circular polarization (glum) and luminescence quantum yield (QY) in circularly polarized luminescence (CPL) systems poses a significant challenge. In this study, we present an innovative strategy utilizing the entropically driven self‐assembly of amphiphilic phosphorescent platinum(II) complexes (L−Pt) with tetraethylene glycol chains, resulting in unique temperature dependencies. The entropically driven self‐assembly of L−Pt leads to a synergistic improvement in phosphorescence emission efficiency (QY was amplified from 15 % at 25 °C to 53 % at 60 °C) and chirality, both in the ground state and the excited state (glum value has been magnified from 0.04×10−2 to 0.06) with increasing temperature. Notably, we observed reversible modulation of phosphorescence and chirality observed over at least 10 cycles through successive heating and cooling, highlighting the intelligent control of luminescence and chiroptical properties by regulating intermolecular interactions among neighboring L−Pt molecules. Importantly, the QY and glum of the L−Pt assembly in solid state were measured as 69 % and 0.16 respectively, representing relatively high values compared to most self‐assembled CPL systems. This study marks the pioneering demonstration of dual thermo‐enhancement of phosphorescence and CPL and provides valuable insights into the thermal effects on high‐temperature and switchable CPL materials. An entropically driven self‐assembled system based on a platinum complex displays a dual enhancement of phosphorescence and chiroptical response, both in the ground state and excited state (glum value increases from 0.04×10−2 to 0.06), upon elevating the temperature of the supramolecular system. The strategy developed in this work overcomes the customary trade‐off between QY and glum, a prevalent challenge in most CPL materials.