The simultaneous recognition mechanism of cations and anions using macrocyclic-iodine structures: insights from dispersion-corrected DFT calculations

Author(s)

Orenha, Renato Pereira ^[1] ; Nagurniak, Glaucio Regis ^[2] ; Colaco, Matheus Cachoeira ^[3] ; Caramori, Giovanni Finoto ^[3] ; Piotrowski, Mauricio Jeomar ^[4] ; de Araujo Batista, Krys Elly ^[4] ; Munoz-Castro, Alvaro ^[5] ; de Almeida Silva, Breno ^[1] ; Esteves, Benjamim Jose ^[1] ; Parreira, Renato Luis Tame ^[1]

Affiliation

^[1] Univ Franca, Nucleo Pesquisas Ciencias Exatas & Tecnol, Franca, SP - Brazil

^[2] Univ Fed Santa Catarina, Dept Ciencias Exatas & Educ, Blumenau, SC - Brazil

^[3] Univ Fed Santa Catarina, Dept Quim, Campus Univ Trindade, CP 476, BR-88040900 Florianopolis, SC - Brazil

^[4] Univ Fed Pelotas, Dept Phys, POB 354, Pelotas, RS - Brazil

^[5] Univ Autonoma Chile, Fac Ingn, Lab Quim Inorgan & Mat Mol, Llano Subercaceaux 2801, Santiago - Chile

• Document type: Journal article
• Source: Physical Chemistry Chemical Physics; v. 22, n. 41, p. 23795-23803, NOV 7 2020.
• Web of Science Citations: 0

Abstract

The recent development of compounds for recognizing ions highlights the applicability of this area. In this work, the simultaneous recognition of cations (Li+, Na+ and K+) and anions (F-, Cl- and I-) using a macrocycle comprising a simple crown ether and an iodine-triazole unit is investigated. The roles of the (i) cation radius, (ii) anion radius, and (iii) electron withdrawing (-CN) and donor (-OH) groups of the receptor in ionic recognition were evaluated. Energy decomposition analysis (EDA) shows that the ion-receptor interactions are attractive and predominantly electrostatic. Molecular electrostatic potential plots and EDA analysis reveal that a decreasing cation radius favors interactions with the oxygen atoms present in the crown ether. A decreasing anion radius increases the sigma-hole interactions with the iodine atoms present in the receptors. In compounds containing -CN and -OH groups, the oxygen atoms in the crown ether show lower ability to interact with the Na+ cation. Nevertheless, in the receptor-OH structure, the Na+MIDLINE HORIZONTAL ELLIPSISOH interactions counterbalance the lower ability of the crown ether oxygens to interact with the Na+ cation. I- recognition is enhanced by the presence of -OH and, more strongly, -CN groups, occurring due to the increased sigma-hole area in the receptor-CN structure, as supported by a C-HMIDLINE HORIZONTAL ELLIPSISI- interaction in the receptor-OH compound. The reported results are useful for the design of compounds with improved capabilities for both cation and anion recognition prior to engaging in exploratory synthesis efforts. (AU)

• FAPESP's process: 11/07623-8 - The use of quantum-mechanical methods to study the bonds and chemical interactions in self-organizing systems with applications in catalysis, medicinal chemistry, electrochromism, energy storage and conversion
• Grantee: Renato Luis Tame Parreira
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 17/24856-2 - The Mechanism of the Substitution Reaction of the Ligand Nitrosyl by Aqua in Ruthenium Coordination Compounds
• Grantee: Renato Pereira Orenha
• Support Opportunities: Scholarships in Brazil - Post-Doctoral