Selective Recognition of Fluoride Anion Using a Li+-Metallacrown Complex

Lehaire, Marie-Line; Scopelliti, Rosario; Piotrowski, Holger; Severin, Kay

doi:10.1002/1521-3773(20020415)41:8<1419::aid-anie1419>3.0.co;2-l

Cited by 142 publications

(18 citation statements)

References 29 publications

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“…Complexes with Ligand N -(2-Pyridylmethyl)- l -alanine. A variety of MCs are known; however, only a few structural examples have been reported for [12-MC-3]. − Recent work by Severin et al has shown that an organometallic analogue [12-MC-3] has been found to be a highly potent ionophore with remarkable affinity for Li + and Na + 12b,4a,, …”

Section: Resultsmentioning

confidence: 99%

Nature of the Reactants and Influence of Water on the Supramolecular Assembly

Wang

Vittal

2003

Inorg. Chem.

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The influences of the nature of reactants and water on the self-assembly of cationic Cu(II) complex structures containing N-(2-pyridylmethyl)glycine (Hpgly) and N-(2-pyridylmethyl)-l-alanine (Hpala) ligands have been investigated. A metallamacrocycle [Cu(6)(pgly)(3)(spgly)(3)] (ClO(4))(6).9H(2)O has been formed by the reaction of [Cu(pgly)(2)].2H(2)O with Cu(ClO(4))(2).6H(2)O. The hexameric cation has Schiff base and reduced Schiff base ligands alternatively bonded to Cu(II) to provide cyclohexane-like conformation with a cavity diameter of 9.4 A. The reaction of Cu(ClO(4))(2).6H(2)O with Hpgly.HCl yielded [Cu(pgly)(H(2)O)](ClO(4)), which is presumed to have 1D coordination polymeric structure. A [K subset [12-MC-3]] metallacrown, [K(ClO(4))(3)[Cu(3)(pala)(3)]](ClO(4)) has been isolated by reacting Cu(ClO(4))(2) with Kpala in MeCN/MeOH. This [K subset [12-MC-3]] metallacrown further reacts with water to form an infinite 1D coordination polymer [Cu(pala)(H(2)O)(ClO(4))](n)(), which can also be obtained by conducting the reaction in aqueous MeOH.

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Section: Resultsmentioning

confidence: 99%

Nature of the Reactants and Influence of Water on the Supramolecular Assembly

Wang

Vittal

2003

Inorg. Chem.

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“…300,301 While the trinuclear Ru(III) metallomacrocycles ( 256 , Figure 28) showed high affinity and selectivity for Li + and Na + ion, 164,302 the Ir(III) macrocycles act as a fluoride ion receptor in which a pre-coordinated lithium ion serves as the binding site. 303 The quantification of the host-guest complexes were done by NMR, electrochemical and colorimetric methods. Extending the same strategy further, they have also designed and synthesized a Ru-based metallomacrocycle for the selective detection of lithium ions in water and in serum by fluorescence spectroscopy.…”

Section: Two-dimensional (2d) Ensemblesmentioning

confidence: 99%

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

2011

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“…Molecular containers are of continuing interest for synthetic chemists due to their realized uses as catalysts, , sorters, sensors, , and in cavity directed synthesis. , Most molecular containers are based on hydrocarbon frameworks . An advantage of inorganic frameworks is their potential rigidity, which should impart size-based selectivity to these supermolecules .…”

Section: Introductionmentioning

confidence: 99%

Structural Chemistry of “Defect” Cyanometalate Boxes: {Cs⊂[CpCo(CN)₃]₄[CpRu]₃} and {M⊂[CpRh(CN)₃]₄[Cp*Ru]₃} (M = NH₄, Cs)

Kuhlman

Rauchfuss

2003

J. Am. Chem. Soc.

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A series of heptametallic cyanide cages are described; they represent soluble analogues of defect-containing cyanometalate solid-state polymers. Reaction of 0.75 equiv of [Cp*Ru(NCMe)3]PF6, Et(4)N[Cp*Rh(CN)3], and 0.25 equiv of CsOTf in MeCN solution produced (Cs subset [CpCo(CN)3]4[Cp*Ru]3)(Cs subset Rh4Ru3). 1H and 133Cs NMR measurements show that Cs subset Rh4Ru3 exists as a single Cs isomer. In contrast, (Cs subset [CpCo(CN)3]4[Cp*Ru]3) (Cs subset Co4Ru3), previously lacking crystallographic characterization, adopts both Cs isomers in solution. In situ ESI-MS studies on the synthesis of Cs subset Rh4Ru3 revealed two Cs-containing intermediates, Cs subset Rh2Ru2+ (1239 m/z) and Cs subset Rh3Ru3+ (1791 m/z), which underscore the participation of Cs+ in the mechanism of cage formation. 133Cs NMR shifts for the cages correlated with the number of CN groups bound to Cs+: Cs subset Co4Ru4+ (delta 1 vs delta 34 for CsOTf), Cs subset Rh4Ru3 where Cs+ is surrounded by ten CN ligands (delta 91), Cs subset Co4Ru3, which consists of isomers with 11 and 10 pi-bonded CNs (delta 42 and delta 89, respectively). Although (K subset [Cp*Rh(CN)3]4[Cp*Ru]3) could not be prepared, (NH4 subset [Cp*Rh(CN)3]4[Cp*Ru]3) (NH4 subset Rh4Ru3) forms readily by NH4+-template cage assembly. IR and NMR measurements indicate that NH4+ binding is weak and that the site symmetry is low. CsOTf quantitatively and rapidly converts NH4 subset Rh4Ru3 into Cs subset Rh4Ru3, demonstrating the kinetic advantages of the M7 cages as ion receptors. Crystallographic characterization of CsCo4Ru3 revealed that it crystallizes in the Cs-(exo)1(endo)2 isomer. In addition to the nine mu-CN ligands, two CN(t) ligands are pi-bonded to Cs+. M subset Rh4Ru3 (M = NH4, Cs) crystallizes as the second Cs isomer, that is, (exo)2(endo)1, wherein only one CN(t) ligand interacts with the included cation. The distorted framework of NH4 subset Rh4Ru3 reflects the smaller ionic radius of NH4+. The protons of NH4+ were located crystallographically, allowing precise determination of the novel NH4...CN interaction. A competition experiment between calix[4]arene-bis(benzocrown-6) and NH4 subset Rh4Ru3 reveals NH4 subset Rh4Ru3 has a higher affinity for cesium.

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Selective Recognition of Fluoride Anion Using a Li+-Metallacrown Complex

Abstract: A redox‐responsive receptor based on a self‐assembled metallamacrocycle is able to selectively bind molecular LiF (see X‐ray crystal structure) and act as a highly selective chemosensor for the detection of fluoride anions by electrochemical means, even in protic solvents.

Cited by 142 publications

References 29 publications

Nature of the Reactants and Influence of Water on the Supramolecular Assembly

Nature of the Reactants and Influence of Water on the Supramolecular Assembly

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

Structural Chemistry of “Defect” Cyanometalate Boxes: {Cs⊂[CpCo(CN)₃]₄[CpRu]₃} and {M⊂[CpRh(CN)₃]₄[Cp*Ru]₃} (M = NH₄, Cs)

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Selective Recognition of Fluoride Anion Using a Li+-Metallacrown Complex

Abstract: A redox‐responsive receptor based on a self‐assembled metallamacrocycle is able to selectively bind molecular LiF (see X‐ray crystal structure) and act as a highly selective chemosensor for the detection of fluoride anions by electrochemical means, even in protic solvents.

Cited by 142 publications

References 29 publications

Nature of the Reactants and Influence of Water on the Supramolecular Assembly

Nature of the Reactants and Influence of Water on the Supramolecular Assembly

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

Structural Chemistry of “Defect” Cyanometalate Boxes: {Cs⊂[CpCo(CN)3]4[Cp*Ru]3} and {M⊂[Cp*Rh(CN)3]4[Cp*Ru]3} (M = NH4, Cs)

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Structural Chemistry of “Defect” Cyanometalate Boxes: {Cs⊂[CpCo(CN)₃]₄[CpRu]₃} and {M⊂[CpRh(CN)₃]₄[Cp*Ru]₃} (M = NH₄, Cs)