Chemically Modified Calixarenes as New Selective Receptors for Monovalent Cations

Schwing, Marie-José; McKervey, M. Anthony

doi:10.1007/978-94-009-2013-2_6

Cited by 18 publications

(5 citation statements)

References 37 publications

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“…Table 3 Crystal data and structure refinement for complexes 1-5 6) 4080( 6) 4525( 5) 4681( 6) 4422( 6) 4030( 5) 4549(5) 391 8 ( 5) 40 1 8 ( 6) 3454( 6) 2735( 7) 2603( 6) 3221( 6) 1769(6) 1 200( 5) 858( 6) 371( 6) 259( 6) 569( 6) 10 1 4 ( 5) 470( 7) 1084( 6) 947( 6) 1505( 6) 2242( 7) 2422(5) 1 796( 5) 3264( 7) 4867( 6) 4261 (I 5) 5 58 1 ( 14) 5121( 21) 3609( 7) 4060( 5) 1878( 5) 2016( 6) 2748( 6) 3283( 6) 3093( 5) 4058( 5) 4243( 5) 4025( 5) 41 36( 6) 4424( 6) 46 5 8( 6) 4588( 5) 4332( 5) 3995( 6) 3416( 5) 3147( 7) 3448( 6) 4074( 5) 3092( 6) 2487(5) 1 86 1 (6) 1339(…”

Section: Resultsunclassified

Versatile cation complexation by a calix[4]arene tetraamide (L). Synthesis and crystal structure of [ML][ClO₄]₂·nMeCN (M = Fe^II, Ni^II, Cu^II, Zn^IIor Pb^II)

Beer¹,

Drew²,

Leeson³

et al. 1995

J. Chem. Soc., Dalton Trans.

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Section: Resultsunclassified

Versatile cation complexation by a calix[4]arene tetraamide (L). Synthesis and crystal structure of [ML][ClO₄]₂·nMeCN (M = Fe^II, Ni^II, Cu^II, Zn^IIor Pb^II)

Beer¹,

Drew²,

Leeson³

et al. 1995

J. Chem. Soc., Dalton Trans.

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“…The complexation of alkali metal and ammonium cations by functionalized calix[n]arenes is a topic of current interest in supramolecular chemistry. − In particular, the efficiency and selectivity of ion recognition by calixarene ligands have been studied in homogeneous solution 1-4 and in membrane transport 5,6 as a function of the calixarene backbone, the nature of the binding groups introduced, and the conformational properties of the calix. More recently calixarene receptors have been also used in monolayers at the water−air interface, − which is becoming a suitable technique to study biomimetic molecular recognition phenomena …”

Section: Introductionmentioning

confidence: 99%

Complexation Properties of p-tert-Butylcalix[6]arene Hexamide in Monolayers at the Water−Air Interface

et al. 1996

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p-tert-Butylcalix[6]arene, CAL6, has been functionalized by the introduction of amide moieties (OCH2CONEt2) on the six phenolic OH groups to give the corresponding hexamide, HXAM, which shows an interesting selectivity toward the guanidinium cation. The present study reports the behavior of HXAM monolayers at the water−air interface as a function of temperature and subphase composition. The parameters obtained from the spreading isotherms (limiting areas, A o, compressibility moduli, C s -1 = (1/A)(∂π/∂A), and changes in the Gibbs free energy upon passing from water to salt subphase, ΔG salt-water) and the surface potential data show that the HXAM assumes a “cone-shaped” conformation. The molecules are in a parallel orientation at the water−air interface with the six amide groups in the water phase. Changes in the subphase from water to salt solutions (NaCl, KCl, CsCl, guanidinium thiocyanate) affect the spreading isotherms but not the surface potential behavior. The results are discussed in terms of the two-dimensional phases of the monomolecular films, the stoichiometry of the complexes with the cations, and the conformations of uncomplexed and complexed HXAM molecules. The comparison of these results with those of the unsubstituted CAL6 behavior shows the high selectivity of HXAM monolayers toward the guanidinium cation.

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“…The ability of carbonyl-containing substituents on the lower rim of calixarenes to act as ligating podands for encapsulation of metal and ammonium cations is now well established. − The majority of studies describe the use of ester, − amide, , and carboxylic acid derivatives . Apart from one published study , the use of ketonic carbonyl groups as potential binding sites on the calixarene substructure is unexplored, despite the greater donicity of ketones as compared with esters.…”

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confidence: 99%

Cation Complexation by Chemically Modified Calixarenes. 11. Complexation and Extraction of Alkali Cations by Calix[5]- and -[6]arene Ketones. Crystal and Molecular Structures of Calix[5]arene Ketones and Na⁺ and Rb⁺ Complexes

Bell¹,

Browne²,

McKee³

et al. 1998

J. Org. Chem.

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A series of four calix[5]arenes and three calix[6]arenes (R-calixarene-OCH(2)COR(1)) (R = H or Bu(t)) with alkyl ketone residues (R(1) = Me or Bu(t)) on the lower rim have been synthesized, and their affinity for complexation of alkali cations has been assessed through phase-transfer experiments and stability constant measurements. The conformations of these ketones have been probed by (1)H NMR and X-ray diffraction analysis, and by molecular mechanics calculations. Pentamer 3 (R = R(1) = Bu(t)) possesses a symmetrical cone conformation in solution and a very distorted cone conformation in the solid state. Pentamer 5 (R = H, R(1) = Bu(t)) exists in a distorted 1,2-alternate conformation in the solid state, but in solution two slowly interconverting conformations, one a cone and the other presumed to be 1,2-alternate, can be detected. X-ray structure analysis of the sodium and rubidium perchlorate complexes of 3 reveal the cations deeply encapsulated by the ethereal and carbonyl oxygen atoms in distorted cone conformations which can be accurately reproduced by molecular mechanics calculations. The phase-transfer and stability constant data reveal that the extent of complexation depends on calixarene size and the nature of the alkyl residues adjacent to the ketonic carbonyls with tert-butyl much more efficacious than methyl.

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Chemically Modified Calixarenes as New Selective Receptors for Monovalent Cations

Cited by 18 publications

References 37 publications

Versatile cation complexation by a calix[4]arene tetraamide (L). Synthesis and crystal structure of [ML][ClO₄]₂·nMeCN (M = Fe^II, Ni^II, Cu^II, Zn^IIor Pb^II)

Versatile cation complexation by a calix[4]arene tetraamide (L). Synthesis and crystal structure of [ML][ClO₄]₂·nMeCN (M = Fe^II, Ni^II, Cu^II, Zn^IIor Pb^II)

Complexation Properties of p-tert-Butylcalix[6]arene Hexamide in Monolayers at the Water−Air Interface

Cation Complexation by Chemically Modified Calixarenes. 11. Complexation and Extraction of Alkali Cations by Calix[5]- and -[6]arene Ketones. Crystal and Molecular Structures of Calix[5]arene Ketones and Na⁺ and Rb⁺ Complexes

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Chemically Modified Calixarenes as New Selective Receptors for Monovalent Cations

Cited by 18 publications

References 37 publications

Versatile cation complexation by a calix[4]arene tetraamide (L). Synthesis and crystal structure of [ML][ClO4]2·nMeCN (M = FeII, NiII, CuII, ZnIIor PbII)

Versatile cation complexation by a calix[4]arene tetraamide (L). Synthesis and crystal structure of [ML][ClO4]2·nMeCN (M = FeII, NiII, CuII, ZnIIor PbII)

Complexation Properties of p-tert-Butylcalix[6]arene Hexamide in Monolayers at the Water−Air Interface

Cation Complexation by Chemically Modified Calixarenes. 11. Complexation and Extraction of Alkali Cations by Calix[5]- and -[6]arene Ketones. Crystal and Molecular Structures of Calix[5]arene Ketones and Na+ and Rb+ Complexes

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Versatile cation complexation by a calix[4]arene tetraamide (L). Synthesis and crystal structure of [ML][ClO₄]₂·nMeCN (M = Fe^II, Ni^II, Cu^II, Zn^IIor Pb^II)

Versatile cation complexation by a calix[4]arene tetraamide (L). Synthesis and crystal structure of [ML][ClO₄]₂·nMeCN (M = Fe^II, Ni^II, Cu^II, Zn^IIor Pb^II)

Cation Complexation by Chemically Modified Calixarenes. 11. Complexation and Extraction of Alkali Cations by Calix[5]- and -[6]arene Ketones. Crystal and Molecular Structures of Calix[5]arene Ketones and Na⁺ and Rb⁺ Complexes