Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2020 Jul 24;11(31):8288-8294.
doi: 10.1039/d0sc03445b.

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

Nam Jung Heo  1 , Ju Ho Yang  1 , Vincent M Lynch  2 , Byoung Joon Ko  3 , Jonathan L Sessler  2 , Sung Kuk Kim  1
Affiliations

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

Nam Jung Heo et al. Chem Sci. .

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.

PubMed Disclaimer

Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Synthesis of receptors 1 and 2.
Fig. 1
Fig. 1. Two different views of the single X-ray crystal structure of receptor 1. Thermal ellipsoids are scaled to the 50% probability level. Most hydrogen atoms are omitted for clarity.
Fig. 2
Fig. 2. Two different views of the single X-ray crystal structure of the TEAHCO3 complex of receptor 1. Thermal ellipsoids are scaled to the 30% probability level. Most hydrogen atoms are omitted for clarity.
Fig. 3
Fig. 3. Partial 1H NMR spectra recorded during the titration of 2 (3 mM) with tetrabutylammonium fluoride (TBAF) in CDCl3. *Denotes the residual CHCl3 peak from the NMR solvent.
Fig. 4
Fig. 4. Partial 1H NMR spectra recorded during the titration of the TEAHCO3 complex of receptor 2 (2·TEAHCO3, 3 mM) with TBAF in CDCl3. The spectra of the TEAF and TBAF complexes of receptor 2 measured in the absence of TEAHCO3 are also shown. *Denotes peaks originating from the NMR solvent or NMR spinning sidebands.
Fig. 5
Fig. 5. Top: Proposed fluoride complexes formed when a mixture of receptor 2 in its ion-free form and its TEAHCO3 complexed form are subject to titration with TBAF. Bottom: Partial 1H NMR spectra recorded during the titration of a mixture of ion-free 2 and its TEAHCO3 complex with TBAF in CDCl3. ·Denotes proton signals corresponding to the TEAHCO3 complex of receptor 2. *Denotes peaks originating from the NMR solvent.
Fig. 6
Fig. 6. Hess diagram showing the binding modes and processes for the formation of the TEAF complex of receptor 2.
Fig. 7
Fig. 7. 1H NMR spectra recorded during the titration of 2 (3 mM) with TEAF in 10% D2O in DMSO-d6.
See this image and copyright information in PMC

References

    1. Sessler J. L., Gale P. A. and Cho W.-S., Anion Receptor Chemistry, ed. J. F. Stoddart, Royal Society of Chemistry, Cambridge, 2006
    2. Bianchi A., Bowman-James K. and García-España E., Supramolecular Chemistry of Anions, Wiley-VCH, New York, 1997
    3. Anion Coordination Chemistry, ed. K. Bowman-James, A. Bianchi and E. García-España, Wiley-VCH, Weinheim, 2011
    1. Beer P. D. Gale P. A. Angew. Chem., Int. Ed. 2001;40:486–516. doi: 10.1002/1521-3773(20010202)40:3<486::AID-ANIE486>3.0.CO;2-P. - DOI - PubMed
    2. Martínez-Máñez R. Sancenán F. Chem. Rev. 2003;103:4419–4476. doi: 10.1021/cr010421e. - DOI - PubMed
    3. Gale P. A. Busschaert N. Haynes C. J. E. Karagiannidis L. E. Kirby I. L. Chem. Soc. Rev. 2014;43:205–241. doi: 10.1039/C3CS60316D. - DOI - PubMed
    4. Wenzel M. Hiscock J. R. Gale P. A. Chem. Soc. Rev. 2012;41:480–520. doi: 10.1039/C1CS15257B. - DOI - PubMed
    5. Gale P. A. Chem. Soc. Rev. 2010;39:3746–3771. doi: 10.1039/C001871F. - DOI - PubMed
    6. Caltagirone C. Gale P. A. Chem. Soc. Rev. 2009;38:520–563. doi: 10.1039/B806422A. - DOI - PubMed
    7. Gale P. A. Caltagirone G. Chem. Soc. Rev. 2015;44:4212–4227. doi: 10.1039/C4CS00179F. - DOI - PubMed
    1. Kang S. O. Begum R. A. Bowman-James K. Angew. Chem., Int. Ed. 2006;45:7882–7894. doi: 10.1002/anie.200602006. - DOI - PubMed
    2. Kang S. O. Llinares J. M. Day V. W. Bowman-James K. Chem. Soc. Rev. 2010;39:3980–4003. doi: 10.1039/C0CS00083C. - DOI - PubMed
    3. Oh J. H. Kim J. H. Kim D. S. Han H. J. Lynch V. M. Sessler J. L. Kim S. K. Org. Lett. 2019;21:4336–4339. doi: 10.1021/acs.orglett.9b01515. - DOI - PubMed
    1. Chen Y. Cann M. J. Litvin T. N. Iourgenko V. Sinclair M. L. Levin L. R. Buck J. Science. 2000;289:625–628. doi: 10.1126/science.289.5479.625. - DOI - PubMed
    2. Krieg B. J. Taghavi S. M. Amidon G. L. Amidon G. E. J. Pharm. Sci. 2014;103:3473–3490. doi: 10.1002/jps.24108. - DOI - PubMed
    3. Vaughan-Jones R. D. Spitzer K. W. Biochem. Cell Biol. 2002;80:579–596. doi: 10.1139/o02-157. - DOI - PubMed
    4. Roos A. Boron W. F. Physiol. Rev. 1981;61:296–434. doi: 10.1152/physrev.1981.61.2.296. - DOI - PubMed
    5. Zippin J. H. Levin L. R. Buck J. Trends Endocrinol. Metab. 2001;12:366–370. doi: 10.1016/S1043-2760(01)00454-4. - DOI - PubMed
    1. Casey J. R. Biochem. Cell Biol. 2006;84:930–939. doi: 10.1139/o06-184. - DOI - PubMed
    2. Liu Y. Wang D.-Ke. Chen L.-M. Biol. Reprod. 2012;86:1–13. - PubMed