Metal–Organic Flexible Glasses Deliver Time‐Chirality‐Color Multi‐Dimensional Photonic Switches

Combining color tunability with high processability in active optical waveguides remains a major challenge, as conventional crystalline materials are fundamentally limited by brittleness and short excited-state lifetimes. Here, we introduce a new class of metal-organic hybrid (MOH) photonic glasses assembled through an evaporation-induced self-assembly strategy, simultaneously achieving time-, space-, and color-resolved photonic capabilities that encompass circularly polarized room-temperature phosphorescence (CPR) and reversible photochromism. The glasses exhibit bright green CPR whose emission color is continuously and dynamically tunable across a broad spectral range through photochromic switching. Mechanistic investigations combining spectroscopic characterization with theoretical analysis attribute the strong CPR to efficient suppression of non-radiative transitions via multiple intermolecular interactions, while photochromism originates from photoinduced radical generation. Their outstanding processability further enables fabrication of large-scale, flexible core-cladding optical fibers that serve concurrently as photonic memory systems and integrated photonic circuits. This work establishes a general design principle for processable photonic glasses that unifies molecular-level design with macroscopic fiber engineering, charting a well-defined path toward next-generation flexible photonic materials and technologies.