ABSTRACT Multicolor fluorescence, typically favored by soft environments, and phosphorescence, which relies on rigid lattices to stabilize triplet excitons, are fundamentally incompatible and hard to coexist within a single material. Here, we report a crown–ether–directed lattice assembly that integrates [HfCl 6 ] 2‒ /[ZrCl 6 ] 2‒ octahedra and DB18C6@M(K + /Rb + ) supramolecular, yielding four unknown organic–inorganic hybrid Hf/Zr halides. Notably, (DB18C6@K) 2 (CH 3 CN) 2 HfCl 6 achieves an exceptional room‐temperature phosphorescence (RTP) quantum yield (Φ p ) of 54.43%, a long lifetime of 0.8 s, and a visually discernible afterglow persisting up to 6 s. Moreover, these materials exhibit excitation–dependent multicolor emission, producing green and blue–white outputs under 302 and 365 nm irradiation, respectively. This unique multimodal luminescence originates from the synergistic interplay between the balanced soft‐rigid lattice provided by the crown‐ether framework and heavy – atom Hf/Zr centers, which facilitates intersystem crossing, enabling both efficient RTP and tunable multichannel pathways. It has been confirmed by the high–pressure synchrotron angle–dispersive x–ray diffraction and Raman results. Overall, this work establishes a heavy–atom–based structural mediation which may offer a generalizable route to high‐efficiency, multichannel, and stimuli‐responsive RTP materials.
ABSTRACT Reduction of [(BDI)SrI] 2 with KC 8 generated in situ a (BDI)Sr I species which enabled the reduction of Ph 3 B to the Ph 3 B 2− dianion (BDI = HC[(Me)C═N‐DIPeP] 2 , DIPeP = 2,6‐(Et 2 CH) 2 ‐phenyl). The product (BDI)Sr(BPh 3 )Sr(BDI) features a Ph 3 B 2− dianion that is bridging two Sr 2+ cations by interaction with one of the Ph rings. This polarizes a large part of the electron density in the bridging Ph ring (NPA charge: −1.53) whereas the B is slightly positive (+0.44). The HOMO of the complex mainly consists of the π*‐orbital in the bridging Ph ring overlapping with Sr d ‐orbitals. However, there is also 18% contribution of the B p ‐orbital. In solution, there is coalescence of 1 H NMR signals of all three Ph rings. Complex (BDI)Sr(BPh 3 )Sr(BDI) can react as a 2 e transfer reagent or as a B‐nucleophile. It reacts with I 2 to Ph 3 B and [(BDI)SrI] 2 . Reaction with Ph 3 B led to formation of a Gomberg‐type dimer. The reaction with PhI is smooth and selectively gave (BDI)Sr(Ph 4 B) and [(BDI)SrI] 2 , likely through direct nucleophilic attack of an electron rich B atom at PhI. Isolation of a complex with the elusive Ph 3 B 2− dianion demonstrates the very high reducing power of in situ generated (BDI)Sr I species.
ABSTRACT Electrocatalysis is essential for renewable energy conversion, yet the mechanisms governing catalytic performance remain poorly understood due to the complex nature of electrochemical interfaces. Advances in nanomaterial synthesis and high‐resolution characterization now allow detailed structural and compositional analysis, but static methods fall short of capturing the dynamic behaviors of active sites during operation. In this review, we focus on the growing role of in situ and operando techniques such as optical, X‐ray, and electron‐based, in resolving catalytic structure and reactivity under real‐life working conditions. These methods offer unparalleled access to the evolution of surface species, reaction intermediates, and interfacial topologies that govern catalytic functions. We highlight how in situ and operando studies have revealed transient phenomena and mechanistic details previously inaccessible, and discuss their critical roles in advancing systems for water splitting, CO 2 /N 2 reduction, and fuel cells related renewable energy applications. Beyond highlighting the real‐time transformations captured by operando and in situ methods, this review underscores how coupling operando datasets with theoretical modeling and machine learning can accelerate mechanistic discovery and enable rational catalyst design. By extracting hidden correlations and guiding closed‐loop experimentation, data‐driven approaches promise to reduce reliance on empirical trial‐and‐error and unlock predictive control over catalytic performance. Taken together, these developments position operando characterization, when coupled with AI‐driven interpretation, as a cornerstone of future energy research, providing a pathway to accelerate discovery, design, and deployment of next‐generation electrocatalysts.
ABSTRACT Bioorthogonality‐activatable optical imaging activates caged or quenched probes via bioorthogonal reactions for disease diagnosis. Although chemiluminescence enables low‐background detection, it has rarely been applied to bioorthogonality‐activatable imaging. Here, we synthesize chemiluminescent tetrazine probes (CLTZs) by coupling a tetrazine acceptor to a phenoxy‐1,2‐dioxetane donor through π‐conjugated vinylene linkers, enabling biomarker and bioorthogonality dual‐locked activation for cancer urine testing. Unlike conventional chemiluminophores, tetrazine in CLTZs mediates an internal‐conversion‐to‐a‐dark‐state quenching mechanism, suppressing chemiluminescence even after phenolate formation. Strong chemiluminescence is restored only when the phenolate form undergoes bioorthogonal reaction with bicyclononyne (BCN), generating pyridazine‐containing donor–π–acceptor chemiluminophores. This unique dark state enables development of an H 2 O 2 and bioorthogonality dual‐locked probe ( H BCP), emitting only when both H 2 O 2 and BCN are present. By engineering BCN into a cancer‐activatable bioorthogonal urinary reporter ( C BUR) that releases renal‐clearable BCN in tumors, a chemiluminescent bioorthogonal pair ( H BCP & C BUR) is created. This pair achieves in vivo tumor imaging with a signal‐to‐background ratio of 438 and detects lung metastasis in early urinary assays with up to 23.9‐fold signal enhancement over healthy mice. This work provides a molecular design for bioorthogonality‐activatable chemiluminescence toward noninvasive, sensitive disease diagnosis.
ABSTRACT A major bottleneck for the practical application of lithium–oxygen (Li–O 2 ) batteries is the high overpotential resulting from sluggish kinetics of oxygen redox chemistry. This kinetic limitation can rise in part from the spin‐state transition barriers in converting triplet oxygen ( 3 O 2 ) into peroxide species, alongside the parasitic generation of singlet oxygen ( 1 O 2 ). Here, we demonstrate that metal–support magnetic interactions can effectively overcome this spin barrier. Using palladium (Pd) nanoparticles anchored on ferrimagnetic CoFe 2 O 4 (CFO) substrates as a model catalyst, we reveal that interfacial magnetic coupling restructures the spin and electronic states of Pd sites, generating spin‐polarized active ensembles with optimized adsorption toward oxygen intermediates. This interfacial spin‐electronic effect promotes the conversion of 3 O 2 into peroxide species while suppressing parasitic 1 O 2 evolution during charging, thereby improving the reversibility of oxygen redox chemistry. As a result, the Pd/CFO catalyst achieves a low charging overpotential of 0.05 V and remarkable energy efficiency (91.2%) under spin alignment. This finding establishes metal–support magnetic interaction as a powerful strategy for controlling spin‐dependent oxygen electrocatalysis, providing a general design principle for catalysts involving multi‐site interactions.
