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

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.