Toward Two‐Dimensional Metallic Topologies in Atomically Precise Nanoclusters

ABSTRACT While topology–property relationships are well established in covalent two‐dimensional (2D) materials, their extension to metallic systems is hindered by the nondirectional nature of metallic bonding and an intrinsic tendency toward three‐dimensional (3D) close‐packed structures. Herein, we develop a Hub‐Driven Ring Fusion (HDRF) strategy for constructing extended metallic topologies beyond discrete motifs. Guided by this strategy, we synthesize an atomically precise Pd 11 nanocluster featuring a rare fused tri‐pentagonal metal‐ring network. Magnetic shielding and nucleus‐independent chemical shift (NICS) analyses reveal pronounced spatial anisotropy and discontinuous shielding distributions, indicating a breakdown of global electronic coherence and the formation of partitioned electronic domains across fused rings. These “topology‐induced electronic domains” connectivity‐governed electronic fragmentation, rather than uniform delocalization, defines the intrinsic electronic landscape of the cluster and clarifies that it is not merely a simple size expansion of Pd 5 . Pd 11 exhibits significantly enhanced performance in the electrocatalytic hydrogenation of nitrobenzene, achieving 98.1% conversion, 97.4% aniline yield, and 99.3% selectivity, outperforming Pd 5 and Pd 8 clusters. Density functional theory (DFT) calculations further demonstrate that the fused tri‐pentagonal topology optimizes electron distribution, enhances interfacial reactivity, and lowers the overall reaction barrier, providing a mechanistic basis for the observed catalytic enhancement.