Coating the fullerene: evaluation of the core–shell interaction nature in a saturated exohedral cuprofullerene

C₆₀ fullerene exhibits a unique structure and properties ideal for forming materials for nanoscale electronic devices. The formation of an exohedral metallofullerene array has been characterized, which reveals a concentric triple core-shell C₆₀@Cu₃₀@Cl₃₆N₁₂ architecture in [C₆₀@Cu₃₀Cl₃₆(Cu(PhCH₂NH₂)₂)₆]^6- (1), involving saturated coordination over the fullerene surface. The calculated interaction between C₆₀ and the fully coated shell is strong, amounting to -675.4 kcal mol^-1, predominantly electrostatic in nature, in contrast to the dispersion-dominated and weaker interaction in the partially coated analogue (-104.5 kcal mol^-1). As a result, in 1, thirty Cu-CC interactions exhibit similar coordination characteristics to copper-ethane complexes. The metallic coating induces a symmetry reduction in the C₆₀ cage (from <i>I</i>_h to <i>T</i>_h), giving rise to three distinct ¹³C NMR shifts, and facilitates substantial charge transfer (1.88e^-) to the fullerene. Notably, a dramatic shift in NICS(0) (-2.08 → -10.9 ppm) reveals a breakdown of the Faraday cage behavior, indicating through-space magnetic shielding effects arising from the outer shell. The fully coated fullerene-based architectures point to tailored modulation of fullerene properties <i>via</i> metal-layer design, advancing prospects for tunable molecular devices.