Abstract
The coordination of divalent and monovalent inorganic anions to synthetic polyammonium receptors is investigated in aqueous solution around neutral pH by titration calorimetry and NMR spectroscopy. High-affinity 1:1 complexes are formed by a pyrrole type cryptand (1) with sulfate and phosphate, characterized by association constants of almost 107 M-1. Affinities close to 105 M-1 are found for polyazacryptands (3 and 4) exhibiting F-/Cl- selectivity. The binding affinities and the anion selectivities are mainly caused by the charges of ligands and anions, which is discussed on the basis of simple calculations of the electrostatic contribution to the anion/receptor interactions. The binding of all investigated anions is exothermic at 298.2 K. The contribution of the large negative ΔH values to the free energy of anion binding of the pyrrole type ligand is partially compensated by marked negative ΔS values. These unfavorable entropic contributions are attributed to the additional inclusion of water molecules in the anion/receptor complexes.
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References
B. Dietrich, Pure Appl. Chem., 65 (1993) 1457.
Supramolecular Chemistry of Anions (A. Bianchi, K. Bowman-James, E. Garcia-Espa_a, <nt>Eds</nt>), Wiley-VCH, New York 1997.
P. D. Beer and P. A. Gale, Angew. Chem. Int. Ed., 40 (2001) 486.
G. Grenningloh, A. Rienitz, B. Schmitt, C. Methfessel, M. Zensen, K. Beyreuther, E. Gundelfinger and H. Betz, Nature, 328 (1987) 221.
P. R. Schofield, M. G. Darlison, N. Fujita, D. R. Burt, F. A. Stephenson, H. Rodriguez, L. M. Rhee, J. Ramachandran, V. Reale, T. A. Glencorse, P. H. Seeburg and E. A. Barnard, Nature, 328 (1987) 221.
B. Dietrich, B. Dillworth, J.-M. Lehn, J.-P. Souchez, M. Cesario, J. Guilhem and C. Pascard, Helv. Chim. Acta, 79 (1996) 569.
K. Worm and F. P. Schmidtchen, Angew. Chem., Int. Ed., 34 (1995) 65.
D. Chen and A. E. Martell, Tetrahedron, 47 (1991) 6895.
G. Morgan, V. McKee and J. Nelson, J. Chem. Soc., Chem. Commun., (1995) 1649.
M. J. Hynes, B. Maubert, V. McKee, R. M. Town and J. Nelson, J. Chem. Soc., Dalton Trans., (2000) 2853.
M. J. S. Dewar, E. G. Zoebisch, E. F. Healy and J. J. P. Stewart, J. Am. Chem. Soc., 107 (1985) 3902.
M. J. S. Dewar and K. M. Dieter, J. Am. Chem. Soc., 108 (1986) 8075.
N. L. Allinger, J. Am. Chem. Soc., 99 (1977) 8127.
T. Wiseman, S. Williston, J. F. Brandts and L.-N. Lin, Anal. Chem., 17 (1989) 131.
E. Grell, E. Lewitzki, A. Schacht and M. Stolz, J. Therm. Anal. Cal., 77 (2004) 471.
R. M. Fuoss, J. Am. Chem. Soc., 80 (1958) 5059.
C. Bremer, H. Ruf and E. Grell, J. Phys. Chem., 102 (1998) 146.
M. Berger and F. P. Schmidtchen, Angew. Chem., Int. Ed., 37 (1998) 2694.
R. M. Smith and A. Martell, Critical Stability Constants, Vol. 4, Plenum Press, New York 1976.
G. Anderegg, Helv. Chim. Acta, 46 (1963) 1833.
P. Jost, R. Schurhammer and G. Wipff, Chem. Eur. J., 6 (2000) 4257.
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Grell, D., Grell, E., Bugnon, P. et al. Molecular Ionics of Anion Receptor Molecules: A Microcalorimetric Study. Journal of Thermal Analysis and Calorimetry 77, 483–495 (2004). https://doi.org/10.1023/B:JTAN.0000038988.19849.bb
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DOI: https://doi.org/10.1023/B:JTAN.0000038988.19849.bb