Solvent‐Mediated Multi‐Factor Structural Modulation for Tunable Phosphorescence in Metal–Organic Frameworks

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Abstract
Independently controlling phosphorescence dynamics while preserving the intrinsic emissive state is essential for establishing mechanistically clear framework‐phosphorescence relationships and rationally developing diverse phosphorescent metal–organic frameworks (MOFs). Yet conventional ligand/metal screening typically alters the emissive center. Herein, a novel solvent‐mediated multi‐factor structural modulation strategy yields five Zn‐based MOFs with tunable dimensionalities (1D, 2D, 3D) from a single metal/ligand system, exhibiting widely tunable phosphorescence lifetimes (12.6–1045.4 ms) and quantum yields (0.2%–16.2%), while retaining broadly similar ligand‐centered green emission, allowing kinetic differences to be attributed primarily to coupled structural variations. Single‐crystal structures reveal dimensional, terminal‐ligand, and guest‐confinement variations governing supramolecular interactions and framework rigidity. Theoretical analysis links these factors to distinct excited‐state localization, while γ/β descriptors link orbital mixing to intersystem crossing and radiative decay. Among the five structures, strong hydrogen bonding and guest confinement in the guest‐containing 2D MOF afford a 1045.4 ms lifetime, whereas semi‐chelate coordination and excited‐state localization in 1D MOF may favor a 16.2% quantum yield. These color‐stable, lifetime‐tunable materials enable covert exclusive‐OR optical encoding featuring parity‐check self‐validation and single‐bit error correction. This paradigm provides new chemical insights into decoupling phosphorescence dynamics from the intrinsic emissive state, enabling mechanistic elucidation and rational construction of multiscale, tailorable phosphorescent MOF systems.
Funding Information
  • National Natural Science Foundation of China (22405011)
  • China Postdoctoral Science Foundation (2026T190251)
  • China Postdoctoral Science Foundation (2026M790009)
  • China Postdoctoral Science Foundation (YJA20250002)

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