Iodide Recognition and Sensing in Water by a Halogen‐Bonding Ruthenium(II)‐Based Rotaxane

Langton, Matthew J.; Marques, Igor; Robinson, Stephen K.; Félix, Vı́tor; Beer, Paul D.

doi:10.1002/chem.201504018

Cited by 86 publications

(92 citation statements)

References 61 publications

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“…Rather, chaotropic anions can be classified as hydrophilic on ion‐solvation scales 107, 108. Classifications of chaotropic ions as hydrophobic, occasionally found in the literature,109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119 are unfortunate because they may lead to incorrect assignments in terms of the underlying driving force for associative processes. Vice versa, hydrophobic ions do actually exist, such as BPh 4 − , (C 2 F 5 ) 3 PF 3 − , and AsPh 4 + ,80, 120, 121, 122 and it is also important not to label these as being superchaotropic47, 51, 52, 123 when sequences of ionic properties, scales for ionic solvation, or reasons for aqueous assembly processes are being developed.…”

Section: Thermochemical Hydration Characteristicsmentioning

confidence: 99%

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The Chaotropic Effect as an Assembly Motif in Chemistry

2018

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Following up on scattered reports on interactions of conventional chaotropic ions (for example, I−, SCN−, ClO4 −) with macrocyclic host molecules, biomolecules, and hydrophobic neutral surfaces in aqueous solution, the chaotropic effect has recently emerged as a generic driving force for supramolecular assembly, orthogonal to the hydrophobic effect. The chaotropic effect becomes most effective for very large ions that extend beyond the classical Hofmeister scale and that can be referred to as superchaotropic ions (for example, borate clusters and polyoxometalates). In this Minireview, we present a continuous scale of water–solute interactions that includes the solvation of kosmotropic, chaotropic, and hydrophobic solutes, as well as the creation of void space (cavitation). Recent examples for the association of chaotropic anions to hydrophobic synthetic and biological binding sites, lipid bilayers, and surfaces are discussed.

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Section: Thermochemical Hydration Characteristicsmentioning

confidence: 99%

“…Accordingly, the unexpectedly high binding affinities of superchaotropic anions and the chaotropic effect as a generic driving force have recently found their entry into the important area of anion recognition 44, 65, 117, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143…”

Section: Examplesmentioning

confidence: 99%

The Chaotropic Effect as an Assembly Motif in Chemistry

2018

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“…Following our previous work, [50,63] the XB interactions were simulated with the inclusion, in the force field parameterisation, of an extra-point of positive charge to represent the s-hole of each iodine atom of the triazolium binding units. [64] Thes tarting binding scenarios of 5·(Cl) 2 and 5·NO 3 À were built assembling the two macrocycles and the bis-iodotriazolium axle central motif in an interlocked orthogonal binding arrangement, in agreement with the structures of analogous XB [2]rotaxane hosts.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…[64] Thes tarting binding scenarios of 5·(Cl) 2 and 5·NO 3 À were built assembling the two macrocycles and the bis-iodotriazolium axle central motif in an interlocked orthogonal binding arrangement, in agreement with the structures of analogous XB [2]rotaxane hosts. [50,63] In addition, in 5·(Cl) 2 , the two chloride anions together with the two macrocycles were initially disposed in ap arallel manner with each anion establishing two hydrogen bonds with asingle isophthalamide binding cleft and one halogen bond with aiodo-triazolium XB binding unit, as shown in Figure 4. Henceforth, the coconformation adopted by the XB [3]rotaxane 5 in this binding arrangement is called A.I n5·NO 3 À the trigonal anion was placed in ap osition consistent with its simultaneous recognition by the two macrocycles and the bis-iodo-triazolium axle central motif.These two anion [3]rotaxane arrangements, illustrated in Figure S27, were subsequently immersed in periodic cubic boxes of as olvent mixture of 1:1 CHCl 3 :CH 3 OH and their dynamic behaviours were ascertained through three MD production runs of 100 ns each.…”

Section: Angewandte Chemiementioning

confidence: 99%

Selective Nitrate Recognition by a Halogen‐Bonding Four‐Station [3]Rotaxane Molecular Shuttle

et al. 2016

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The synthesis of the first halogen bonding [3]rotaxane host system containing abis-iodo triazolium-bis-naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate,hydrogen carbonate and dihydrogen phosphate oxoanions and chloride,and exhibits enhanced recognition of anions relative to ah ydrogen bonding analogue.T his elaborate interlocked anion receptor functions via an ovel dynamic pincer mechanism where upon nitrate anion binding,b oth macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodotriazolium station anion recognition sites to form aunique 1:1 stoichiometric nitrate anion-rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the 1 HNMR anion binding results.The prevalence of negatively charged species in biology and in the environment has deemed the development of synthetic anion receptors capable of their strong and selective recognition an important field of chemical research. [1][2][3] Thenitrate anion in particular is an environmental pollutant when leeched into lakes and rivers resulting from anthropogenic overuse of fertilizers or by acid rain.[4] Medically,a no ver exposure to nitrate via contaminated drinking water is associated with the formation of carcinogenic nitrosamines and ar ange of diseases such as methemoglobinemia (blue baby syndrome) in infants. [5] Thedesign of synthetic receptors capable of the selective recognition of nitrate is ac hallenge because of the anions inherent low affinity for hydrogen bonds and high energy of solvation.[6] To date only arelatively small number of nitrateselective tripodal acyclic,m acrocyclic and cage-like host systems have been reported that utilise convergent hydrogen bonding (HB) and/or anion-p interactions to recognise the oxoanion in polar organic solvents. [7][8][9][10][11][12][13][14][15][16][17][18][19] Thec hallenge of developing synthetic receptors that can rival the anion recognition properties of biotic systems relies upon the arrangement of at hree-dimensional convergent array of numerous HB donor groups in an optimized geometry for recognition of the complementary guest. [20,21] To meet this challenge we have exploited anion-templation to construct interlocked host structures [22,23] whose unique threedimensional cavities encapsulate anionic guest species.While during the past two decades HB has been widely exploited in anion receptor design, halogen bonding (XB), [24][25][26][27] the attractive highly directional interaction between an electron-deficient halogen atom and aL ewis base,h as only recently begun to be utilised for anion recognition. Of the relatively few examples of XB anion receptors reported to date,i ti sn oteworthy that all display promising,a nd significantly contrasting, anion recognition behaviour when compared ...

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“…The starting binding scenarios of 5⋅(Cl) 2 and 5⋅NO 3 − were built assembling the two macrocycles and the bis‐iodo‐triazolium axle central motif in an interlocked orthogonal binding arrangement, in agreement with the structures of analogous XB [2]rotaxane hosts 50, 63. In addition, in 5⋅(Cl) 2 , the two chloride anions together with the two macrocycles were initially disposed in a parallel manner with each anion establishing two hydrogen bonds with a single isophthalamide binding cleft and one halogen bond with a iodo‐triazolium XB binding unit, as shown in Figure 4.…”

mentioning

confidence: 91%

Selective Nitrate Recognition by a Halogen‐Bonding Four‐Station [3]Rotaxane Molecular Shuttle

et al. 2016

Self Cite

View full text Add to dashboard Cite

The synthesis of the first halogen bonding [3]rotaxane host system containing a bis‐iodo triazolium‐bis‐naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo‐triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion–rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the 1H NMR anion binding results.

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Iodide Recognition and Sensing in Water by a Halogen‐Bonding Ruthenium(II)‐Based Rotaxane

Cited by 86 publications

References 61 publications

The Chaotropic Effect as an Assembly Motif in Chemistry

The Chaotropic Effect as an Assembly Motif in Chemistry

Selective Nitrate Recognition by a Halogen‐Bonding Four‐Station [3]Rotaxane Molecular Shuttle

Selective Nitrate Recognition by a Halogen‐Bonding Four‐Station [3]Rotaxane Molecular Shuttle

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