Recent Advances in Luminescent Hydrogen‐Bonded Organic Frameworks (HOFs): Linker Design, Phosphorescence, and Smart Responsiveness

ABSTRACT

Hydrogen‐bonded organic frameworks (HOFs) combine crystallinity with dynamic reversibility, yet their weak interlayer interactions pose a fundamental challenge: how to suppress nonradiative decay without sacrificing structural adaptability. This review critically surveys recent progress in luminescent HOFs across three interconnected pillars: fluorescence enhancement through linker rigidification, AIE core integration, and heterostructure engineering; ultralong room‐temperature phosphorescence via heavy atom effects, framework confinement, and triplet to singlet Förster resonance energy transfer; and stimuli‐responsive emission switching upon physical stimuli, such as light, electricity, force, and temperature, as well as chemical triggers including ions, gases, and pH. Distinct from previous accounts, we analyze structure‐property relationships rather than cataloging examples, provide quantitative comparisons through summary tables, and include a dedicated section on key photophysical mechanisms to aid nonspecialist readers. We further identify persistent bottlenecks, including aqueous stability, scalable synthesis, and device integration, and outline a roadmap toward next‐generation HOFs for chemical sensing, bioimaging, and optoelectronics.