Premium
Cage‐size effects on the encapsulation of P 2 by fullerenes
Author(s) -
Sabater Enric,
Solà Miquel,
Salvador Pedro,
Andrada Diego M.
Publication year - 2023
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26884
Subject(s) - fullerene , pnictogen , molecule , chemistry , computational chemistry , carbon group , chemical physics , crystallography , nanotechnology , stereochemistry , materials science , organic chemistry , physics , group (periodic table) , superconductivity , quantum mechanics
Abstract The classic pnictogen dichotomy stands for the great contrast between triply bonding very stable N 2 molecules and its heavier congeners, which appear as dimers or oligomers. A banner example involves phosphorus as it occurs in nature as P 4 instead of P 2 , given its weak π‐bonds or strong σ‐bonds. The P 2 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 P 2 inside the fullerene cages. Given the size differences between P 2 and P 4 , we show that the fullerenes C 70 –C 100 are suitable cages to side exclude P 4 and host only one molecule of P 2 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.