Radical‐Induced Hour‐Level Afterglow and Efficient Circularly Polarized Luminescence From Metal Halide Hybrid Glasses

ABSTRACT Molecular hybrid glasses have emerged as a fourth category in glass chemistry and materials, offering new possibilities beyond the synthesis limits and property constraints of traditional inorganic (nonmetallic), organic, and metallic systems. A key advancement in this field is the integration of multifunctionality into monolithic glasses, essential for next‐generation smart optical display and information storage, but progress remains its nascent stage. Here, we introduce a family of large‐scale monolithic photoactive hybrid glasses with enhanced environmental sustainability and no reliance on rare earth elements. Incorporating amine derivatives into a zero‐dimensional organic‐inorganic halide glass enables persistent luminescence (PersL) over hours—surpassing state‐of‐the‐art hybrid glasses based on RTP or TADF. Importantly, we disruptively elucidate the underlying mechanisms of radical‐induced PersL (RIP) and precise photochromism in these glasses, addressing a long‐standing scientific challenge. Additionally, embedding chiral molecules in the glass matrix induces efficient circularly polarized luminescence (CPL), achieving an optical dissymmetry factor (g lum ) of up to 1.1 × 10 −2 —setting a new benchmark for chiral hybrid glasses. This work not only advances the design and synthesis of high‐performance photofunctional hybrid glasses integrating PersL, photochromism, and CPL, but also expands their potential applications in information security, semiconductor inks, UV printing, and chiroptical devices.