The simultaneous recognition mechanism of cations and anions using macrocyclic–iodine structures: insights from dispersion-corrected DFT calculations,Physical Chemistry Chemical Physics

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The simultaneous recognition mechanism of cations and anions using macrocyclic–iodine structures: insights from dispersion-corrected DFT calculations
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2020-10-06 , DOI: 10.1039/d0cp04291a
Renato Pereira Orenha _{1,

2,

3,

4} , Glaucio Régis Nagurniak _{4,

5,

6,

7} , Matheus Cachoeira Colaço _{4,

8,

9,

10} , Giovanni Finoto Caramori _{4,

8,

9,

10} , Maurício Jeomar Piotrowski _{4,

11,

12,

13} , Krys Elly de Araújo Batista _{4,

11,

12,

13} , Alvaro Muñoz-Castro _{14,

15,

16,

17,

18} , Breno de Almeida Silva _{1,

2,

3,

4} , Benjamim José Esteves _{1,

2,

3,

4} , Renato Luis Tame Parreira _{1,

2,

3,

4}

Affiliation

Núcleo de Pesquisas em Ciências Exatas e Tecnológicas
Universidade de Franca
Franca
Brazil
Universidade Federal de Santa Catarina
Departamento de Ciências Exatas e da Educação
Blumenau
Departamento de Química
Universidade Federal de Santa Catarina, Campus Universitário Trindade
Florianópolis
Department of Physics
Federal University of Pelotas
Pelotas
Laboratorio de Química Inorgánica y Materiales Moleculares
Facultad de Ingenieria
Universidad Autonoma de Chile
Llano Subercaceaux
San Miguel

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 σ-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⁺⋯OH 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 σ-hole area in the receptor–CN structure, as supported by a C–H⋯I⁻ 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.

中文翻译：

利用大环碘结构同时识别阳离子和阴离子的机制：色散校正DFT计算的见解

用于识别离子的化合物的最新发展突出了该领域的适用性。在这项工作中，阳离子（李的同时识别⁺，钠⁺和K ⁺）和阴离子（F ^-，氯^-我^-）使用包含简单冠醚和碘-三唑单元的大环进行了研究。评估了（i）阳离子半径，（ii）阴离子半径和（iii）受体的吸电子（-CN）和供体（-OH）在离子识别中的作用。能量分解分析（EDA）表明，离子-受体相互作用具有吸引力，并且主要是静电的。分子静电势图和EDA分析表明，阳离子半径的减小有利于与冠醚中存在的氧原子的相互作用。减小的阴离子半径会增加与受体中存在的碘原子的σ-孔相互作用。在含有–CN和–OH基团的化合物中，冠醚中的氧原子与Na ⁺相互作用的能力较低阳离子。然而，在受体-OH结构中，Na ⁺ ⋯OH相互作用抵消了冠醚氧与Na ⁺阳离子相互作用的较低能力。我^-识别是通过-OH的存在，并且更强烈地，-CN基团，存在的由于在受体- CN结构的增加的σ孔面积，由C-H⋯我所支持的增强的^-在受体相互作用-OH化合物。报道的结果可用于设计具有探索性合成努力之前具有改善的阳离子和阴离子识别能力的化合物。

更新日期：2020-10-17

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