Enhanced sodium cation binding by electrochemically reduced nitrobenzene-substituted lariat ethers

Kaifer, Ángel E.; Echegoyen, Luis; Gustowski, Deborah A.; Goli, Deepa M.; Gokel, George W.

doi:10.1021/ja00362a023

Cited by 72 publications

(24 citation statements)

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“…To investigate this issue in more detail, binding affinities for guests were estimated using methods first developed for redox active crown and cryptand hosts [59–63] . In this model, the electrochemical potentials of a free and bound host ( E H and E HG respectively) and the binding affinity of its oxidation states ( K a red and K a ox respectively) are related in this way:

true \frac{K_{a} ((), r, e, d)}{K_{a} ((), o, x)} = e^{((), \frac{F}{R T}) (() E_{1 / 2} (H G) - E_{1 / 2} (H))}

…”

Section: Resultsmentioning

confidence: 99%

Being Positive is Not Everything – Experimental and Computational Studies on the Selectivity of a Self‐Assembled, Multiple Redox‐State Receptor that Binds Anions with up to Picomolar Affinities

Thomas

Zubi

Alnafisah

et al. 2021

Chemistry A European J

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The interaction of the self-assembled trinuclear ruthenium bowl 1 3 + , that displays three other accessible oxidation states, with oxo-anions is investigated. Using a combination of NMR and electrochemical experimental data, estimates of the binding affinities of 1 4 + , 1 5 + , and 1 6 + for both halide and oxo-anions were derived. This analysis revealed that, across the range of oxidation states of the host, both high anion binding affinities (> 10 9 M À 1 for specific guests bound to 1 6 + ) and high selectivities (a range of > 10 7 M À 1 ) were observed. As the crystal structure of binding of the hexafluorophosphate anion revealed that the host has two potential binding sites (named the α and β pockets), the host-guest properties of both putative binding sites of the bowl, in all of its four oxidation states, were investigated through detailed quantum-based computational studies. These studies revealed that, due to the interplay of ion-ion interactions, charge-assisted hydrogen-bonding and anion-π interactions, binding to the α pocket is generally preferred, except for the case of the relatively large and lipophilic hexafluorophosphate anionic guest and the host in the highest oxidation states, where the β pocket becomes relatively favourable. This analysis confirms that host-guest interactions involving structurally complex supramolecular architectures are driven by a combination of non-covalent interactions and, even in the case of charged binding pairs, simple ion-ion interactions alone cannot accurately define these recognition processes.

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true \frac{K_{a} ((), r, e, d)}{K_{a} ((), o, x)} = e^{((), \frac{F}{R T}) (() E_{1 / 2} (H G) - E_{1 / 2} (H))}

…”

Section: Resultsmentioning

confidence: 99%

Being Positive is Not Everything – Experimental and Computational Studies on the Selectivity of a Self‐Assembled, Multiple Redox‐State Receptor that Binds Anions with up to Picomolar Affinities

Thomas

Zubi

Alnafisah

et al. 2021

Chemistry A European J

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“…Our approach to cation-binding enhance ment and potentially to "molecular switching" involves the incorporation of an electron-deficient side arm that can be reversibly reduced to its corre sponding anion radical (49,50). Upon reduction, the anionic side arm, if correctly disposed geometrically, is able to interact strongly with the macroring-bound cation (Scheme I).…”

Section: Cation-binding Enhancement By Reduced Lariat Ethers and Crypmentioning

confidence: 99%

Cation Effects on Solvents, Ligands, and Nucleophiles

Gokel

Echegoyen

Arnold

et al. 1987

Advances in Chemistry

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Macrocyclic polyether compounds having one (lariat ethers) or two (bibracchial lariat ethers, BiBLEs) donor-group-bearing side arms exhibit Na+-, K+-, NH4+-, and Ca 2+ -binding affinities and selec tivities different from those of the unsubstituted macrocycles. Mac rocycles utilizing a nitrogen atom as the point of attachment (pivot atom) show generally higher flexibility and binding strength than compounds having the sidearm(s) attached at a carbon (carbon pivot). The more flexible and less polar compounds favor K + over the more charge-dense cations irrespective of hole size. The cation bind ing involves both the macroring and the side arms. This fact is demonstrated for solutions as well as the solid state. Ν-pivot BiBLEs can be prepared by a very convenient single-step cyclization or by a two-step approach that is more conventional but that affords high yields of product. Both lariat ethers and BiBLEs can be electrochemically "switched" to alter the cation-binding affinities and strengths.

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“…The redox centers incorporated into crown ethers are of two types based on whether they undergo reduction to form anionic hosts (e.g. nitrobenzyl [1,2] or quinone [3][4][5]) or oxidation to form cationic hosts (e.g. ferrocene [6] or tetrathiafulvalene [7]).…”

Section: Introductionmentioning

confidence: 99%

“…As such, this class of hosts offers the opportunity for strong mutual interaction between the redox center and guest in redox-switching and sensing applications. While a number of previous studies [1][2][3][4][5][6][9][10][11][12] have monitored the complexation ability of redox-active hosts through electrochemical measurements (primarily cyclic voltammetry), these data either do not or, typically, have not been used to provide detailed structural information. Electrochemical simulations of CV curves can be used to postulate reaction mechanisms but, in the absence of additional data, typically not used to confirm proposed mechanisms.…”

Section: Introductionmentioning

confidence: 99%

On the oxidation of Wurster’s reagent and the Wurster’s crown analog of 15-crown-5 in the presence of alkali metal cations

Backer

Hureau

Depriester

et al. 2008

Journal of Electroanalytical Chemistry

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Enhanced sodium cation binding by electrochemically reduced nitrobenzene-substituted lariat ethers

Cited by 72 publications

References 0 publications

Being Positive is Not Everything – Experimental and Computational Studies on the Selectivity of a Self‐Assembled, Multiple Redox‐State Receptor that Binds Anions with up to Picomolar Affinities

Being Positive is Not Everything – Experimental and Computational Studies on the Selectivity of a Self‐Assembled, Multiple Redox‐State Receptor that Binds Anions with up to Picomolar Affinities

Cation Effects on Solvents, Ligands, and Nucleophiles

On the oxidation of Wurster’s reagent and the Wurster’s crown analog of 15-crown-5 in the presence of alkali metal cations

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