Can Functionalized Cucurbituril Bind Actinyl Cations Efficiently? A Density Functional Theory Based Investigation

Abstract

The feasibility of using cucurbituril host molecule as a probable actinyl cation binders candidate is investigated through density functional theory based calculations. Various possible binding sites of the cucurbit[5]uril host molecule to uranyl are analyzed and based on the binding energy evaluations, μ(5)-binding is predicted to be favored. For this coordination, the structure, vibrational spectra, and binding energies are evaluated for the binding of three actinyls in hexa-valent and penta-valent oxidation states with functionalized cucurbiturils. Functionalizing cucurbituril with methyl and cyclohexyl groups increases the binding affinities of actinyls, whereas fluorination decreases the binding affinities as compared to the native host molecule. Surprisingly hydroxylation of the host molecule does not distinguish the oxidation state of the three actinyls.

Computational study on the interactions of mustard gas with cucurbituril macrocycles

“…Furthermore, host–guest interaction studies between the guest rodamine B and kiton red S to CB[7] show that the guest molecules are stabilized by the hydrogen bonding . The binding efficiency of actinyl atom toward CBs shows that the formation of ‐coordination is energetically favorable compared with the ‐coordination, and the vibration spectra was helpful in differentiating the isomers . Recently, binding and the nature of interaction of halide ion with CBs, hemi‐cucurbit[6]uril (hm‐CBs), and bambus[6]uril (BUs) were studied using density functional theory (DFT) calculations .…”

Speciation of uranium‐mandelic acid complexes using electrospray ionization mass spectrometry and density functional theory

“…Such T-shaped complexes have been reported in solution phase and in protein environments. [34,36] As can be seen in the computed potential energy diagram ( Supplementary Fig S7, Supporting Information), the dimeric species 18 is favored by 4 kcal mol -1 over the monomeric UO 2 (MA) 2 species.…”

“…[30,31] A similar combination of functional and basis sets was previously used to predict accurate geometries and energetics for several uranyl complexes. [24,[32][33][34][35][36][37][38][39] To verify whether the obtained structures correspond to the potential energy minima, analytical frequency calculations were carried out using the AOFORCE module as implemented in TURBOMOLE version 6.3.1 (Karlsruhe, Germany). [40] Finally, binding free energies were calculated at 298.15 K after incorporating thermal and non-thermal corrections into the electronic energies.…”

Formation of aqua and tetraammine Cu(II) complexes inside the cavities of cucurbit[6,8]urils: A DFT forecast

“…So far, there have been relatively few publications devoted to quantum-chemical studies of interactions between guest particles and cucurbiturils, in particular, those concerned with the modeling of the formation of the inclusion compounds. [1,3,10,[42][43][44][45][46][47][48][49][50][51] A significant part of this research has been devoted to the exploration of the intrinsic mechanism of CB[n] formation and elucidation of the causes of predominant yield of CB [6] during the synthesis of CB[n] homologues. [1,3,20,21] In other relevant studies, quantum-chemical calculations have been used primarily to determine properties and characteristics of individual macrocycles that cannot be determined experimentally.…”