Anion binding in the C3v-symmetric cavity of a protonated tripodal amine receptor: potentiometric and single crystal x-ray studies

Bose, Purnandhu ; Ravikumar, I. ; Ghosh, Pradyut (2011) Anion binding in the C3v-symmetric cavity of a protonated tripodal amine receptor: potentiometric and single crystal x-ray studies Inorganic Chemistry, 50 (21). pp. 10693-10702. ISSN 0020-1669

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic2011502?jour...

Related URL: http://dx.doi.org/10.1021/ic2011502

Abstract

Tris(2-aminoethyl)amine (tren) based pentafluorophenyl-substituted tripodal L, tris[[(2,3,4,5,6-pentafluorobenzyl)amino]ethyl]amine receptor is synthesized in good yield and characterized by single crystal X-ray diffraction analysis. Detailed structural aspects of binding of different anionic guests toward L in its triprotonated form are examined thoroughly. Crystallographic results show binding of fluoride in the C3v-symmetric cavity of [H3L]3+ where spherical anion fluoride is in tricoordinated geometry via (N–H)+···F interaction in the complex [H3L(F)]·[F]2·2H2O, (3). In the case of complexes [H3L(OTs)]·[OTs]2, (4) and [H3L(OTs)]·[NO3]·[OTs], (5), tetrahedral p-toluenesulphonate ion is engulfed in the cavity of [H3L]3+ via (N–H)+···O interactions. Interestingly, complex [(H3L)2(SiF6)]·[BF4]4·CH3OH·H2O, (6) shows encapsulation of octahedral hexafluorosilicate in the dimeric capsular assembly of two [H3L]3+ units, via a number of (N–H)+···F interactions. The kinetic parameters of L upon binding with different anions are evaluated using a potentiometric study in solution state. The potentiometric titration experiments in a polar protic methanol/water (1:1 v/v) binary solvent system show high affinity of the receptor toward more basic fluoride and acetate anions, with a lesser affinity for other inorganic anions (e.g., chloride, bromide, nitrate, sulfate, dihydrogenphosphate, and p-toluenesulphonate).

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