Unprecedented Carbon-like Nanomaterials and Bandgap-Engineered Perovskites from an Octet-Rule-Derived ONa ₆ Supercarbon Building Block

The rational design of superatomic architectures mimicking carbon's versatility remains a fundamental challenge yet holds promising potential for programmable quantum materials and functional devices. Herein, an octet-rule-derived open-shell ONa₆ superatom, a carbon analogue with a perfectly matching electronic configuration, was designed to form methane-like supramolecules (Na₄@ONa₆ and Br₄@ONa₆) through directional SP³ superhybrid bonding. This enables a bottom-up assembly of 15 cluster-based carbon-like architectures, including metallic diamond and graphite analogues with ultralow work functions, alongside thermally stable perovskite semiconductors featuring linearly tunable band gaps. These supercarbons replicate elemental carbon's electronic signature while transcending natural allotropes, serving as quantum building blocks for atomically precise 2D lattices and 3D frameworks. Demonstrating programmable functionality from electrocatalysis to robust visible-light seawater splitting photocatalysts, our approach systematically maps structural evolution from atomic clusters to functional materials. These findings may unlock an expanded design space for carbon-transcending functional materials and chemically integrated quantum devices, offering unprecedented opportunities in superatomic chemistry for designing advanced functional materials through the engineering of atomic clusters.