The anionic recognition mechanism based on polyol and boronic acid receptors

Orenha, Renato Pereira; Cintra, Claudia Haber; Peixoto, Letícia Bermudes; Silva, Éder Henrique da; Caramori, Giovanni F.; Ortolan, Alexandre O.; Piotrowski, Maurício J.; Parreira, Renato L. T.

doi:10.1039/c9nj06200a

Cited by 4 publications

(7 citation statements)

References 52 publications

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“…2 This binding type was also found for a different arylboronic acid 4a and was confirmed by theoretical calculations. 6 Surprisingly, 1 that is more electrophilic and lacks the second OH group binds this anion through the hydrogen bonding. The course of 1 H NMR titration of 1 by H 2 PO 4 − shown in Figure S4a essentially coincides with that by acetate.…”

Section: ■ Results and Discussionmentioning

confidence: 97%

“…Previously, the B97-D3 functional with the 6-31+G(d) or Def2TZVP basis set was used to optimize both Hbonded and coordinate anion-PBA complexes. 6 However, the B97-D functional was found to perform less satisfactory for the dative bonding in substituted boranes, for which significantly better results were obtained with the M06-2X functional. 26 The performance of M06-2X for H-bonded interactions is similar to that of the B97-D functional, 27 and therefore, we chose to use the M06-2X functional with the Def2TZVP basis set for structure optimization.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The association of PBA with H 2 PO 4 – , in contrast to the association with acetate, was reported to proceed through the coordinate bonding . This binding type was also found for a different arylboronic acid and was confirmed by theoretical calculations . Surprisingly, 1 that is more electrophilic and lacks the second OH group binds this anion through the hydrogen bonding.…”

Section: Resultsmentioning

confidence: 99%

“…4 The type of anion binding is essential for applications of boronic acids in catalysis, 5 and it is also the subject of computational analysis. 6 The preferable acidity type, Lewis or Brønsted, was investigated recently for boranolcontaining naphthoid heterocycles. 7 Also, results involving the selectivity of anion recognition by boronic acids are of interest for studies of hydrogen bonding interactions of boronic acids with other Lewis bases of different types.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The majority of reported boronic acid-based anion sensors operate via the coordinate bonding and are designed for detection of fluoride, but recently, the hydrogen bonding mode is also exploited in the design of anion receptors . The type of anion binding is essential for applications of boronic acids in catalysis, and it is also the subject of computational analysis . The preferable acidity type, Lewis or Brønsted, was investigated recently for boranol-containing naphthoid heterocycles .…”

Section: Introductionmentioning

confidence: 99%

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Anion Recognition by Benzoxaborole

et al. 2022

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The binding types (H-bonding or coordinate) and stability constants for complexes of 11 mono- and di-anions with benzoxaborole (1) were determined by 1H and 11B NMR titrations in DMSO or MeCN. Compared to phenylboronic acid (PBA), 1 is a stronger Lewis acid and a poorer H-bond donor with only one B-OH group, which is expected therefore to recognize anions mostly through the coordinate bonding. This is the case however only with F–, HPO4 2–, and PhPO3 2– anions, which are coordinately bonded to 1, and partially with SO4 2–, which forms only the H-bonded complex with PBA, but both H-bonded and coordinate complexes with 1. The majority of tested anions (AcO–, PhPO3H–, (PhO)2PO2 –, Cl–, and Br–) form H-bonded complexes with both 1 and PBA, whereas H2PO4 – changes the binding mode from coordinate for PBA to H-bonded for 1. The preferable binding type for each anion is confirmed by calculations of DFT-optimized structures of the anion complexes of 1. The preferable binding type can be rationalized considering the effects of the steric hindrance, more significant for the coordinate bonding, and of increased anion basicity, which is favorable for both binding types, but enhances the strength of coordinate bonding more significantly than the strength of H-bonding.

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Section: ■ Results and Discussionmentioning

confidence: 97%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Anion Recognition by Benzoxaborole

et al. 2022

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The strength and selectivity of perfluorinated nano‐hoops and buckybowls for anion binding and the nature of anion‐π interactions

Fan

Dang

et al. 2022

J Comput Chem

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Perfluorinated cycloparaphenylenes (F‐[n]CPP, n = 5–8), boron nitride nanohoop (F‐[5]BNNH), and buckybowls (F‐BBs) were proposed as anion receptors via anion‐π interactions with halide anions (Cl−, Br− and I−), and remarkable binding strengths up to −294.8 kJ/mol were computationally verified. The energy decomposition approach based on the block‐localized wavefunction method, which combines the computational efficiency of molecular orbital theory and the chemical intuition of ab initio valence bond theory, was applied to the above anion‐π complexes, in order to elucidate the nature and selectivity of these interactions. The overall attraction is mainly governed by the frozen energy component, in which the electrostatic interaction is included. Remarkable binding strengths with F‐[n]CPPs can be attributed to the accumulated anion‐π interactions between the anion and each conjugated ring on the hoop, while for F‐BBs, additional stability results from the curved frameworks, which distribute electron densities unequally on π‐faces. Interestingly, the strongest host was proved to be the F‐[5]BNNH, which exhibits the most significant anisotropy of the electrostatic potential surface due to the difference in the electronegativities of nitrogen and boron. The selectivity of each host for anions was explored and the importance of the often‐overlooked Pauli exchange repulsion was illustrated. Chloride anion turns out to be the most favorable anion for all receptors, due to the smallest ionic radius and the weakest destabilizing Pauli exchange repulsion.

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