Anilate Tethered Neutral Tetrahedral Pd(II) Cages Exhibiting Selective Encapsulation of Xylenes and Mesitylene

Abstract The design of porous materials for the recognition of multiple hydrocarbons is highly desirable for the energy‐efficient separation and recognition of chemical feedstock. Herein, three new iso‐structural porous discrete metal–organic cages of formula {[Pd 3 (N i Pr) 3 PO] 4 (R‐AN) 6 } (R‐AN=anilate linkers) for the selective recognition of substituted aromatic hydrocarbons are reported. The tetrahedral cages 1 , 2 , and 3 containing anilate, chloranilate, and bromanilate linkers exhibited selective encapsulation of mesitylene, o ‐xylene, and p ‐xylene, respectively, over other analogous aromatic hydrocarbons. These selective encapsulations were driven by the variations in the portal diameters present at each of these cages and their interactions with the hydrocarbon guests. These observations are supported by mass spectrometry, NMR studies, and theoretical binding‐energy calculations.