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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

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

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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]
Total Authors: 10
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
Total Affiliations: 5
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