Three-dimensional (3D) aromaticity provides a powerful framework for understanding the stability and electronic structures of superatomic clusters, yet how such aromaticity evolves during atom-by-atom structural growth remains poorly understood. Herein, we report two endohedral zirconium-antimony Zintl clusters, [Zr@Sb12]2- and [Zr@Sb13]3-, that offer a rare one-atom comparison of nuclearity-dependent aromaticity and photodynamics. Structural and bonding analyses reveal that [Zr@Sb12]2- behaves as an integrated Sb12 framework rather than three discrete Sb4 fragments coordinated to Zr. Adaptive natural density partitioning (AdNDP) and magnetic-response analyses establish a closed-shell S2P6 superatomic configuration, giving rise to pronounced spherical all-metal aromaticity. In contrast, incorporation of one additional Sb atom reorganizes the framework into a cage-like [Zr@Sb13]3- cluster, disrupts superatomic shell closure, and produces an S2P4 configuration with strongly attenuated spherical aromaticity. Femtosecond transient absorption (fs-TA) spectroscopy further reveals that the aromatic [Zr@Sb12]2- cluster exhibits markedly longer-lived excited-state species than [Zr@Sb13]3-. These findings establish a direct structure-aromaticity-dynamics relationship, demonstrating that single-atom control of cluster nuclearity can regulate not only ground-state aromatic stabilization but also excited-state robustness in all-metal superatoms.
Designing second-sphere microenvironments that promote proton-coupled electron transfer is central to catalysis yet difficult to achieve in porous solids, such as metal–organic frameworks (MOFs). Here, we report an end-to-end workflow that couples literature-guided large-language-model (LLM) reasoning with real-time experimental feedback to propose, test, and refine microenvironment designs in MOF photocatalysts. The system mined and fused three domains (namely, photocatalytic H2 production, hydrogenases and enzyme-mimetic catalysis) and deduced the hypothesis that placing basic, hydrogen-bonding groups near catalytic centers would facilitate water activation and proton transfer. The hypothesis was instantiated by postsynthetic modification of UiO-67, generating 31 Pt@UiO-67-X variants and evaluating them across six closed-loop iterations on an automated platform. The search converged on Pt@UiO-67-30 (8-quinolinecarboxylic acid), which delivered 2.33 mmol g–1 h–1, a ∼36-fold improvement over the parent material; in a larger, optimally illuminated reactor the same catalyst reached 12.48 mmol g–1 h–1 while preserving the library’s rank order. Photoluminescence quenching, enhanced photocurrent, and reduced impedance are consistent with faster charge separation, and first-principles calculations are consistent with reduced proton-transfer barriers via N···H hydrogen-bond networks. These results establish a practical microenvironment-engineering strategy in MOFs and show how LLM-guided knowledge fusion with experiment-in-the-loop reasoning can systematize and accelerate targeted discovery of functional materials.
Yi-Ming Zhao, Tao Song, Lin-Jiang Chen et al.· Journal of the American Chem...· 0 citations
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