Yifu Chen

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.

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.

Rh-mediated diazoacetate polymerization has garnered significant attention as an effective approach to obtain highly syndiotactic, completely functionalized carbon chain polymers. However, improving catalytic efficiency of the Rh complex by using readily available reagents remains challenging. Herein, we report an unprecedented catalytic system consisting of RhI(cod)Cl]2 (cod = 1,5-cyclooctadiene) and organoamine that can polymerize various diazoacetates to afford well-defined syndiotactic polycarbenes in high yields, with large molar masses and narrow dispersities. A combination of thorough mechanistic characterization and DFT calculations reveals that the chain propagation may start with [(cod)RhI-H(NEt3)] species, formed by the oxidative addition of [(cod)RhI-Cl(NEt3)] with trace ethanol in reaction solvent and subsequent reductive β-H elimination. Optically active helical polymers also form from achiral bulky diazoacetates when enantiomerically pure amines serve as ancillary reagents. Those polymers without traditional luminophore exhibit interesting circularly polarized photoluminescence. The present work demonstrates a promising route to explore high-performance Rh-based catalysts for carbene polymerization and develop advanced functional materials.

Achieving dynamic motions in molecular crystals with both long-range displacement and precise control remains a central challenge. Herein, we report a light-driven rolling motion in twisted single crystals of 9-cyanoanthracene, representing a new motility paradigm that combines structural asymmetry with directional actuation. Under UV irradiation, straight crystals exhibit limited bending due to anisotropic lattice expansion from localized [4 + 4] photodimerization. However, when twisted into helices, they roll rapidly and directionally toward the light source. Systematic investigations reveal that rolling is driven by a transient, light-induced shift in the center of mass, which generates torque through the misalignment of gravitational and normal forces. The rolling velocity can be finely tuned through external parameters including light intensity and incidence angle, as well as internal structural features including crystal length, width, and helical pitch. While the handedness of helicity does not affect rolling velocity under unconstrained conditions, introducing a lateral constraint with a fine wire reveals a distinct helicity-dependent deflection in the rolling trajectory. Specifically, when rolling toward the light, left-handed helices consistently deviate to the right, whereas right-handed helices deviate to the left. This helicity-biased rolling arises from asymmetric contact forces during rolling and highlights the role of contact mechanics in translating structural chirality into directional motion. This work establishes rolling as a conceptually novel mode of crystal actuation, demonstrating how structural chirality and photoreactivity can be synergistically harnessed to impart directionality to dynamic motion. Our findings lay the foundation for developing advanced smart materials with complex, programmable functionalities based on molecular crystals.

Natural polymers have been used as stereoselective crystallization inhibitors benefiting from their intrinsic hierarchical chirality. However, the chirality of their constituent unit is intrinsically immutable due to the natural biosynthetic origin of biopolymers, fundamentally limiting their versatility, as they cannot be synthetically inverted to target the opposite enantiomer. Herein, we designed a magnetic nanosplitter by grafting cellulose acetate phthalate onto Fe₃O₄ nanoparticles to selectively interact with the crystals of one enantiomer, enabling them to form magnetized crystals that can be efficiently separated from their racemic conglomerate with an external magnetic field. This approach enabled the resolution of racemic nimodipine, simultaneously yielding considerable quantities of magnetic S-crystals and nonmagnetic R-crystals. It should be mentioned that using pristine natural polymer derivatives can only obtain crystals of one enantiomer, the less pharmacologically active R-crystals. Further structural investigation revealed that the chain length of the polymer and the size of Fe₃O₄ nanoparticles significantly influence the resolution of the nanosplitters. When containing cellulose acetate phthalate with a molecular weight above 20 kDa and Fe₃O₄ cores sized between 5 and 14 nm, the optimal performance has been achieved, producing S- and R-enantiomers with 82 ee% and 92 ee%, respectively, and a combined yield of 40%. This work pioneers a magnetically driven separation strategy that can be seamlessly integrated into automated chiral separation platforms.

A series of multi-color persistent phosphorescent crystalline materials were constructed using the inherently green, heavy atom-free γ-cyclodextrin metal–organic frameworks through guest encapsulation. Owing to the macrocycles effectively suppressing guest aggregation and forming rigid environments via potassium ion assembly, the material exhibits a lifetime and phosphorescence quantum yield of 553 ms and 8.19%, respectively. Furthermore, upon encapsulation with commercial dyes such as sodium fluorescein and rhodamine B, full-color afterglow emissions were achieved through phosphorescence energy transfer. This work provides a universal method for designing and preparing environmentally friendly phosphorescent materials, overcoming the inherent limitations of degradation and recyclability in organic room-temperature phosphorescent compounds.

Biomimetic materials of BaCO₃–SiO₂ biomorphs hybridized with organic dyes were developed to visualize the functional differences among various morphologies. The helicoid microstructures with curved-growth exhibit multistage fluorescence coding characteristics, while the conical microstructures with flat-growth visually exhibit white light emission behavior that is visible due to tricolor spectral superposition.

Jumping crystals of racemic mixtures of asparagine monohydrate have been presented in this contribution to emphasize the key role of molecular chirality in governing the direction of macroscopic motions. When heated at the specific faces of the single crystals, a pair of enantiomorphs jump in opposite directions, which are further utilized for chiral resolution. The hydrogen-bonded networks between asparagine molecules in a specific direction provide oriented channels for the escape of water molecules during the dehydration, serving as a foundation for the directional crystal jumping. Our findings not only lay the foundation for the future creation of directed actuation systems based on dynamic crystals but shall also guide the efforts to reveal the correlation between chirality and motion across diverse realms of knowledge.