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Capture and displacement-based release of the bicarbonate anion by calix[4]pyrroles with small rigid straps.

ABSTRACT: Two-phenoxy walled calix[4]pyrroles 1 and 2 strapped with small rigid linkers containing pyridine and benzene, respectively, have been synthesized. ¹H NMR spectroscopic analyses carried out in CDCl₃ revealed that both of receptors 1 and 2 recognize only F^- and HCO₃ ^- among various test anions with high preference for HCO₃ ^- (as the tetraethylammonium, TEA⁺ salt) relative to F^- (as the TBA⁺ salt). The bound HCO₃ ^- anion was completely released out of the receptors upon the addition of F^- (as the tetrabutylammonium, TBA⁺ salt) as a result of significantly enhanced affinities and selectivities of the receptors for F^- once converted to the TEAHCO₃ complexes. Consequently, relatively stable TEAF complexes of receptors 1 and 2 were formed via anion metathesis occurring within the receptor cavities. By contrast, the direct addition of TEAF to receptors 1 and 2 produces different complexation products initially, although eventually the same TEAF complexes are produced as via sequential TEAHCO₃ and TBAF addition. These findings are rationalized in terms of the formation of different ion pair complexes involving interactions both inside and outside of the core receptor framework.

SUBMITTER: Heo NJ

PROVIDER: S-EPMC8163245 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature

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Capture and displacement-based release of the bicarbonate anion by calix[4]pyrroles with small rigid straps.

Heo Nam Jung NJ Yang Ju Ho JH Lynch Vincent M VM Ko Byoung Joon BJ Sessler Jonathan L JL Kim Sung Kuk SK

Chemical science 20200724 31

Two-phenoxy walled calix[4]pyrroles 1 and 2 strapped with small rigid linkers containing pyridine and benzene, respectively, have been synthesized. 1H NMR spectroscopic analyses carried out in CDCl3 revealed that both of receptors 1 and 2 recognize only F- and HCO3 - among various test anions with high preference for HCO3 - (as the tetraethylammonium, TEA+ salt) relative to F- ...[more]

PMID: 34094182

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Project description:The importance of noncovalent interactions in the realm of biological materials continues to inspire efforts to create artificial supramolecular polymeric architectures. These types of self-assembled materials hold great promise as environmentally stimuli-responsive materials because they are capable of adjusting their various structural parameters, such as chain length, architecture, conformation, and dynamics, to new surrounding environments upon exposure to appropriate external stimuli. Nevertheless, in spite of considerable advances in the area of responsive materials, it has proved challenging to create synthetic self-assembled materials that respond to highly disparate analytes and whose environmentally induced changes in structure can be followed directly through both various spectroscopic and X-ray diffraction analyses. Herein, we report a new set of artificial self-assembled materials obtained by simply mixing two appropriately chosen, heterocomplementary macrocyclic receptors, namely a tetrathiafulvalene-functionalized calix[4]pyrrole and a bis(dinitrophenyl)-meso-substituted calix[4]pyrrole. The resulting polymeric materials, stabilized by combination of donor-acceptor and hydrogen bonding interactions, undergo dynamic, reversible dual guest-dependent structural transformations upon exposure to two very different types of external chemical inputs, namely chloride anion and trinitrobenzene. The structure and dynamics of the copolymers and their analyte-dependent responsive behavior was established via single crystal X-ray crystallography, SEM, heterocomplementary isodesmic analysis, 1- and 2D NMR, and dynamic light scattering spectroscopies. Our results demonstrate the benefit of using designed heterocomplementary interactions of two functional macrocyclic receptors to create synthetic, self-assembled materials for the development of "smart" sensory materials that mimic the key biological attributes of multianalyte recognition and substrate-dependent multisignaling.

Dataset Information

Capture and displacement-based release of the bicarbonate anion by calix[4]pyrroles with small rigid straps.

Publications

Capture and displacement-based release of the bicarbonate anion by calix[4]pyrroles with small rigid straps.

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