Cage-size effects on the encapsulation of P2 by fullerenes

The classic pnictogen dichotomy stands for the great contrast between triply bonding very stable N₂ molecules and its heavier congeners, which appear as dimers or oligomers. A banner example involves phosphorus as it occurs in nature as P₄ instead of P₂, given its weak π-bonds or strong σ-bonds. The P₂ synthetic value has brought Lewis bases and metal coordination stabilization strategies. Herein, we discuss the unrealized encapsulation alternative using the well-known fullerenes' capability to form endohedral and stabilize otherwise unstable molecules. We chose the most stable fullerene structures from C_n (n = 50, 60, 70, 80) and experimentally relevant from C_n (n = 90 and 100) to computationally study the thermodynamics and the geometrical consequences of encapsulating P₂ inside the fullerene cages. Given the size differences between P₂ and P₄, we show that the fullerenes C₇₀–C₁₀₀ are suitable cages to side exclude P₄ and host only one molecule of P₂ with an intact triple bond. The thermodynamic analysis indicates that the process is favorable, overcoming the dimerization energy. Additionally, we have evaluated the host-guest interaction to explain the origins of their stability using energy decomposition analysis.