Benzene-Ni₁₀S₂₀ Interaction. Host-Guest Features and Nuclear Magnetic Resonance Patterns toward Prototypical Metal-Based Active Cavities

The formation of active pores for the formation of metal-organic frameworks is relevant in materials science, encouraging the design of metal-based host structures. Here, we explore the features leading to the arene incorporation into Ni₁₀S₂₀ frameworks via computational methods. The resulting host-guest aggregation involves favorable interaction energies in the range of ∼ 30 kcal/mol, given by the similar contribution from electrostatic, orbital, and London stabilizing interactions and their interplay to steric repulsions, which rules the resulting orientation of the arene moiety into the Ni₁₀S₂₀ backbone. In addition, palladium and platinum counterparts were evaluated, suggesting related capabilities for group X metal-based cavities. Such properties can be further tuned by variation of the M₁₀ backbone and side functional groups, leading to suitable metallic cavities as prototypical pores to be included in metal-organic frameworks (MOFs) for the incorporation of volatile organic compounds (VOCs) units. In addition, smaller and larger cavity sizes given by related M₈S₁₆ and M₁₂S₂₄ hosts decrease largely the interaction toward benzene, quenching effective sequestering capabilities. Thus, the size of ten-metal cavities is proper for further fixation of benzene into metal-organic active sites. Calculated nuclear magnetic patterns suggest a deshielding shift for incorporated arene units, which are useful features to probe diffusion and orientation of the incoming VOCs. Thus, exploration of group X tiara-like structures may stimulate further applications toward sensing and treatment of different VOC species for designing versatile MOFs.