Coordination‐Triggered Disassembly of Robust Two‐Dimensional Fullerene Frameworks via Intercage C─C σ‐Bond Scission

Two‐dimensional fullerene frameworks such as Mg 4 C 60 and its metal‐free derivative 2D‐C 60 are densely cross‐linked all‐carbon lattices, in which each C 60 cage is tethered to six neighbors through eight intercage C─C σ‐bonds. Formed under high‐temperature conditions (ca. 500°C–600°C), these junction‐rich architectures are generally resistant to post‐synthetic lattice editing or recovery of intact fullerene building blocks. However, we show here that mild transition‐metal coordination can unlock these frameworks under mild solution conditions by cleaving covalent intercage C─C bonds. Treating Mg 4 C 60 with W(CO) 4 (Ph 2 PCH 2 ) 2 leads to measurable depolymerization and time‐dependent formation of molecular C 60 . NiCl 2 (PMe 3 ) 2 promotes substantially more efficient cleavage and enables direct detection of a cleavage intermediate ( m / z = 899), supporting coordination‐linked bond‐scission pathway. Density functional theory shows that C 60 –M–C 60 bridge formation increases the exothermicity for intercage C─C bond scission, and rationalizes the stronger thermodynamic driving force for Ni‐catalytic system relative to W‐catalytic system. Furthermore, Mg 2+ removal markedly suppresses depolymerization, indicating that Mg intercalation promotes junction opening through MgCl 2 formation and charge‐state modulation. These results establish coordination‐triggered intercage bond cleavage as a strategy for lattice editing and programmable disassembly in carbon‐rich 2D frameworks.