Computational Design of Zinc Single-Atom Catalysts in Lantern Organic Framework.

The design of the metal-support interface is fundamental to the performance of single-atom catalysts (SACs). Here, we present a comprehensive computational study by using Density Functional Theory (B3LYP-D3/LANL2DZ for zinc atoms and 6-31+G(d) for other nonmetal atoms) in Zinc-embedded Lantern Organic Frameworks (Zn@LOFs) to resolve this design. By systematically comparing sp- and sp3-bridging motifs, we reveal a critical structural dichotomy: while flexible sp3-frameworks favor endo-configuration, rigid sp-bridging systems introduce a unique kinetic trap that stabilizes accessible exo-configuration. Crucially, agglomeration analysis confirms that the sp-LOF architecture could suppress ZnZn clustering. Beyond stability, we demonstrate precise electronic tunability; endo-Znn@sp-LOFs leverage metal-ligand π-conjugation to significantly narrow the HOMO-LUMO gap, whereas endo-Znn@sp3-LOF affects the gap slightly. Furthermore, electron transport analysis based on Yoshizawa's orbital rules confirms that these constructs maintain good molecular conductance between two ends of the framework-protected Zn-Zn metal chains (10-2 to 10-3 G0; Log[G0] from -2 to -3), despite smaller values in comparison to the free-standing zinc metal chains. Moreover, the predicted gas adsorption behavior indicates that CO2 is predicted to interact more strongly than CO, with adsorption strength modulated by the LOF motifs and the presence and position of Zn centers. These findings establish Zn@LOFs not merely as passive supports, but as tunable, dual-function platforms capable of integrating potential single-atom catalysis with efficient charge transport.