Changjiang Yu

α‐Hydroxymethylated and α‐formylated BODIPYs are valuable fluorescent dyes and synthetic intermediates, yet their direct and controllable preparation from common α‐methyl‐substituted precursors remains challenging. Herein, we report a controlled copper‐catalyzed oxygenation of methyl BODIPYs that enables oxidation‐level‐divergent synthesis of hydroxymethylated and formylated dyes. Using a CuI/2,2′‐bipyridine/Na ₂ CO ₃ system in DMSO, α‐methyl BODIPYs were selectively converted into mono‐hydroxymethylated derivatives under mild conditions. By modifying the reaction parameters and substrate structures, the oxidation level could be further advanced to provide dihydroxymethylated and diformylated BODIPYs in a tunable manner. Preliminary control experiments are consistent with a copper‐mediated oxygenation pathway involving α‐methyl C─H activation and divergent transformation of peroxide‐type intermediates. The hydroxymethylated products largely retain the characteristic absorption and fluorescence features of the parent dyes, whereas formylated derivatives show more pronounced electronic modulation, including bathochromically shifted absorption and emission. This work provides a concise and oxidation‐level‐tunable late‐stage oxygenation strategy for expanding the chemical space of BODIPY dyes.

Aromatic ring-fusion induces activation energy modulation to convert BOPSH fluorophores into heavy-atom-free triplet photosensitizers.

We report a compact N,O,O‐chelated tetracoordinate boron platform (BSBHYs) assembled by a modular one‐pot strategy that independently varies the aldehyde and boronic‐acid components while embedding a strong dimethylamino donor to enhance charge transfer (CT) modulation. Remarkably, these boron chelates achieve an uncommon combination of large Stokes shifts (>3000 cm ⁻¹ ) and pronounced aggregation‐induced emission (AIE). Spectroscopic measurements and density functional theory calculations reveal that the distorted N,O,O coordination geometry promotes a CT‐modulated emissive state and substantial excited‐state relaxation, accounting for the large Stokes shifts, whereas the AIE turn‐on arises from restriction of intramolecular rotation in the condensed phase, which suppresses motion‐assisted nonradiative decay. The calculations further connect donor–acceptor orbital separation with oscillator strength, identify an optically allowed higher singlet state feeding emission via internal conversion, and indicate minimal intersystem crossing. This work establishes a structure–motion–electronic‐state framework for emission control in N,O,O‐boron luminogens.

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We report a novel class of electron-donating boron-chelated salicylhydrazone (BOSHY) fluorophores synthesized through an efficient "two-step, one-pot" condensation strategy. These structurally versatile dyes incorporate a stereogenic boron center within a rigid 6,7-fused bicyclic architecture, demonstrating remarkable dual-state emission characteristics with high quantum yields (up to 95% in solution and 74% in the solid state) and large Stokes shifts up to 7200 cm^-1, along with promising chiroptical activity. Notably, selected BOSHY derivatives display outstanding specificity for lipid droplet imaging in live cells.

Rapid polymerization controlled by visible light holds great potential for advancing 3D printing technologies. However, a significant challenge limiting the implementation of visible-light-activated polymerizations is its low efficiency compared to UV light driven processes. To address this, we developed a series of visible-light-activatable organoboron (BOSHY) complexes featuring salicylaldehyde azine ligands for rapid cationic polymerization. These BOSHYs featuring different brominated BOSHY catalyze the polymerization of epoxides under 405 nm LED light in three-component systems with iodonium salt and amine, achieving a 78% epoxy conversion in just 52 s at low intensity irradiation of 50 mW cm^-2. Additionally, the mechanism of photopolymerization involves the formation of cations by EDB, which initiates the polymerization process. The triplet state lifetime (15.4-23.5 μs) indicates effective intersystem crossing, enabling efficient energy and electron transfer reactions. Experiments confirm nearly 100% electron transfer due to the extended triplet state lifetime. This study not only introduces novel BOSHY derivatives for cationic polymerization but also elucidates the reaction kinetics analysis of the photopolymerization, significantly expanding the use of visible light LEDs as an alternative to UV light in photopolymerization.

Circularly polarized luminescence (CPL) materials have attracted significant attention owing to their unique luminescent properties and their broad range of applications. However, challenges remain, including controlling helical assembly, mitigating aggregation‐caused quenching, and balancing luminescence quantum yield ( Φ _PL ) with g values. Here, the study reports the synthesis of a novel asymmetric, spiranic O‐organoboranes bearing isoindolyl‐indolenine scaffold (BBI) with axial chirality through BINOL substitution, as well as its supramolecular assembly and surfactant‐regulated tunable CPL behaviors. The newly designed BBI dye shows relative weak luminescence with a quantum yield of 10% in toluene. Supramolecular assembly in acetonitrile/water co‐solvents exhibit an obvious aggregation‐induced emission (AIE) process, leading to the formation of spherical nanostructures with red‐shifted orange‐yellow CPL (554 nm, g = 0.012, Φ _PL = 7%). Moreover, a surfactant sodium dodecyl sulfonate (SDS) can promote the aggregation of BBI in pure deionized water, producing nanofibers with blue‐shifted yellow CPL (536 nm, g = 0.006, Φ _PL = 13%). Crystal growth in toluene/hexane and SDS aqueous/acetonitrile systems reveals chiral crystals with the P ₂₁₂₁₂₁ space group, offering insights into chirality amplification. This demonstrates the ability to precisely control CPL properties through assembly parameters, with X‐ray single‐crystal analysis providing additional understanding of chirality regulation.