Counteranion-controlled water cluster recognition in a protonated octaamino cryptand

Lakshminarayanan, P. S. ; Kumar, D. Krishna ; Ghosh, Pradyut (2005) Counteranion-controlled water cluster recognition in a protonated octaamino cryptand Inorganic Chemistry, 44 (21). pp. 7540-7546. ISSN 0020-1669

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Structural aspects of binding of water cluster and halides in the octaamino cryptand L (1,4,11,14,17,24,29,36-octaazapentacyclo[,92.19,22231,34]tetratetraconta-6(43),7,9(44),19(41),20,22(42),31(39),32,34(40)-nonaene, N(CH2CH2NHCH2-p-xylyl-CH2NHCH2CH2)3N) in a protonated state were examined. Crystallographic results show binding of the acyclic quasiplanar water tetramer [H4L(H2O)4](I)4·2.57H2O (1) in a tetraprotonated cryptand L having an iodide counteranion, where two water molecules reside inside the two tren-based cavity, bridged by a third water molecule, and a fourth external water molecule is hydrogen bonded to the bridged water molecule. In the case of complexes [H6L(Br)][(Br)6H]·4H2O·2HBr (2) and [H6L(Cl)][(Cl)6H]·10.86H2O (3), a single bromide and chloride occupied, respectively, the inside of the cryptand cavity, where L is in a hexaprotonated state. Monotopic recognition of bromide/chloride was observed at the center of the cryptand cavity where halides show C−H···halide interactions instead of the N−H···halide interactions reported in the ditopic complexes of halides with the same cryptand, 5 and 6. Thermal analyses on 1−3 were carried out, and the data obtained distinctly differentiate water cluster complex 1 from the anion-encapsulated cryptates 2 and 3. This study represents the first example of anion-controlled cluster formation inside the cavity of a cryptand.

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Source:Copyright of this article belongs to American Chemical Society.
ID Code:101855
Deposited On:23 Jan 2017 11:31
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