Tiara-like Complexes acting as Iodine Encapsulating Agents: The Role of M···I Interactions in [M(μ-SCH₂CO₂Me)₂]₈⊂I₂ (M = Ni, Pd, Pt) Inclusion Compounds

Abstract

A proposed series of tiara-like complexes [M(μ-SCH 2 CO 2 Me) 2 ] 8 (where M = Ni, Pd, Pt) are here studied through DFT methodologies prompted by the synthesis of the palladium parent and their potential application in iodine encapsulation from spent nuclear fuel. Their hollow structure with a suitable cavity size, and the presence of several transition-metal centers capable to directly interact with an I 2 molecule through noncovalent forces, make them attractive inclusion agents. Herein, an energy decomposition analysis reveals that forces responsible for keeping the guest molecule in the inner cavity are mainly electrostatic; a remarkable feature given, in principle, the neutral nature of both the host and guest species, offering us an interesting study case where the electronic cloud distortion of the binding sites and iodine atoms can be estimated and related to the intensity of the host−guest interactions. Our results shed light into the application of the nickel tiara-like host as an alternative to the reported [Pd(μ-SCH 2 CO 2 Me) 2 ] 8 system. This research can be useful for further evaluation of nickel-based iodine sequestering agents prior to engaging in explorative synthesis efforts.

Stabilizing Role of Halide Ions in Endohedral [20]Silafulleranes: Insights from DFT Calculations toward Silicon Nanocages

“…and other covering higher-order interactions (i.e., dipole–dipole, dipole–quadrupole, quadrupole–quadrupole, etc.) following a protocol recently applied to inclusion compounds displaying metallic centers. ,, Then, the central halide ions (Cl – , Br – , I – ) are replaced by their isoelectronic noble gas counterparts (Ar, Kr, Xe), thus enabling only the rise of the higher-order forces. The comparison of the electrostatic terms for each series (1 – (Δ E elec NG /Δ E elec X ))% allows us to quantify the contribution of ion–multipole electrostatic forces into Δ E elec .…”

Dibenzyl Disulfide Adsorption on Cationic Exchanged Faujasites: A DFT Study

“…Finally, a Noncovalent Interactions Analysis (NCI), as proposed by Yang and coworkers, was conducted by using the NCI code [41,42] to describe more precisely the different types of noncovalent interactions such as π-cation. The suitability of this methodology to explain host-guest interactions in metal-containing systems has been reported previously [42,43].…”

Advances in bonding and properties of inorganic systems from relativistic calculations in Latin America

“…The use of the nickel tiara‐like host as an alternative to the reported [Pd( μ ‐SCH 2 CO 2 Me) 2 ] 8 system is discussed . This research can be useful for further evaluation of nickel‐based iodine chelating agents prior to engaging into explorative synthesis efforts . The formation and bonding properties of the related [Ni( μ ‐SCH 3 ) 2 ] n ( n = 4,5,6) systems have been also accounted for …”

“…[74] This research can be useful for further evaluation of nickel-based iodine chelating agents prior to engaging into explorative synthesis efforts. [73] The formation and bonding properties of the related [Ni(μ-SCH 3 ) 2 ] n (n = 4,5,6) systems have been also accounted for. [75] Mendizabal and coworkers studied the noncovalent interaction between several d 10 -d 10 macrocycles and arene fragments, denoting the nature of their formation.…”

“…Heavier cases of host systems have been observed to be capable to encapsulate iodine, showing the key role of M⋯I interactions in [M( μ ‐SCH 2 CO 2 Me) 2 ] 8 ⊂ I 2 ( M = Ni, Pd, Pt) systems, with useful applications in iodine encapsulation from spent nuclear fuel. Energy decomposition analysis establishes that forces responsible for keeping the guest molecule in the inner cavity are mainly of electrostatic nature, which is remarkable given the nature of both the host and guest species.…”