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Design of a Neutral Macrocyclic Ionophore: Synthesis and Binding Properties for Nitrate and Bromide Anions

2002; Wiley; Volume: 2002; Issue: 17 Linguagem: Inglês

10.1002/1099-0690(200209)2002

1434-193X

Rainer Herges, Anton Dikmans, Umasish Jana, Felix Köhler, Peter G. Jones, Ina Dix, Tom Fricke, Burkhard König,

Analytical Chemistry and Sensors

European Journal of Organic ChemistryVolume 2002, Issue 17 p. 3004-3014 Full Paper Design of a Neutral Macrocyclic Ionophore: Synthesis and Binding Properties for Nitrate and Bromide Anions Rainer Herges, Rainer Herges rherges@oc.uni-kiel.de Institut für Organische Chemie der Universität Kiel Otto-Hahn-Platz 4, 24098 Kiel, Germany, Fax: (internat.) + 49-(0)431/880-1558Search for more papers by this authorAnton Dikmans, Anton Dikmans Institut für Organische Chemie der Universität Kiel Otto-Hahn-Platz 4, 24098 Kiel, Germany, Fax: (internat.) + 49-(0)431/880-1558Search for more papers by this authorUmasish Jana, Umasish Jana Institut für Organische Chemie der Universität Kiel Otto-Hahn-Platz 4, 24098 Kiel, Germany, Fax: (internat.) + 49-(0)431/880-1558Search for more papers by this authorFelix Köhler, Felix Köhler Institut für Organische Chemie der Universität Kiel Otto-Hahn-Platz 4, 24098 Kiel, Germany, Fax: (internat.) + 49-(0)431/880-1558Search for more papers by this authorPeter G. Jones, Peter G. Jones Institut für Anorganische und Analytische Chemie der Technischen Universität Braunschweig, 38106 Braunschweig, GermanySearch for more papers by this authorIna Dix, Ina Dix Institut für Anorganische und Analytische Chemie der Technischen Universität Braunschweig, 38106 Braunschweig, GermanySearch for more papers by this authorTom Fricke, Tom Fricke Institut für Organische Chemie, Universität Regensburg 93040 Regensburg, Germany Fax: (internat.) + 49-(0)941/943-1717Search for more papers by this authorBurkhard König, Burkhard König Burkhard.Koenig@chemie.uni-regensburg.de Institut für Organische Chemie, Universität Regensburg 93040 Regensburg, Germany Fax: (internat.) + 49-(0)941/943-1717Search for more papers by this author Rainer Herges, Rainer Herges rherges@oc.uni-kiel.de Institut für Organische Chemie der Universität Kiel Otto-Hahn-Platz 4, 24098 Kiel, Germany, Fax: (internat.) + 49-(0)431/880-1558Search for more papers by this authorAnton Dikmans, Anton Dikmans Institut für Organische Chemie der Universität Kiel Otto-Hahn-Platz 4, 24098 Kiel, Germany, Fax: (internat.) + 49-(0)431/880-1558Search for more papers by this authorUmasish Jana, Umasish Jana Institut für Organische Chemie der Universität Kiel Otto-Hahn-Platz 4, 24098 Kiel, Germany, Fax: (internat.) + 49-(0)431/880-1558Search for more papers by this authorFelix Köhler, Felix Köhler Institut für Organische Chemie der Universität Kiel Otto-Hahn-Platz 4, 24098 Kiel, Germany, Fax: (internat.) + 49-(0)431/880-1558Search for more papers by this authorPeter G. Jones, Peter G. Jones Institut für Anorganische und Analytische Chemie der Technischen Universität Braunschweig, 38106 Braunschweig, GermanySearch for more papers by this authorIna Dix, Ina Dix Institut für Anorganische und Analytische Chemie der Technischen Universität Braunschweig, 38106 Braunschweig, GermanySearch for more papers by this authorTom Fricke, Tom Fricke Institut für Organische Chemie, Universität Regensburg 93040 Regensburg, Germany Fax: (internat.) + 49-(0)941/943-1717Search for more papers by this authorBurkhard König, Burkhard König Burkhard.Koenig@chemie.uni-regensburg.de Institut für Organische Chemie, Universität Regensburg 93040 Regensburg, Germany Fax: (internat.) + 49-(0)941/943-1717Search for more papers by this author First published: 12 August 2002 https://doi.org/10.1002/1099-0690(200209)2002:17 3.0.CO;2-OCitations: 67Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat Abstract A macrocyclic neutral ionophore 8 (X = O) capable of binding weakly coordinating anions such as nitrate and bromide in DMSO solution has been designed by a stepwise, deductive approach. The optimum geometrical arrangement of the hydrogen bond donor sites in the target ionophore was determined by DFT calculations. From these data, a suitable macrocyclic molecular framework was constructed. The 24-membered macrocyclic ionophore was synthesized by standard macrocyclization methods. NMR titrations revealed molecular complexes with defined 1:1 stoichiometries in DMSO for 8 (X = O) with nitrate, hydrogensulfate, acetate, cyanide, iodide, and bromide ions, while dihydrogenphosphate, sulfate, and chloride ions yielded aggregates of higher stoichiometry. The nitrate binding constants of 8 (X = O) are substantial for a neutral ionophore with defined binding sites in pure DMSO solution. Bromide ions, which have a similar ion radius, are bound with an even higher affinity. Chloride is obviously too small, and iodine too large, to form 1:1 complexes. The binding motif of 8 (X = O) was compared with related molecules of similar structure, such as 8 (X = S) and 19. As predicted from calculations, the small structural variations give rise to a complete loss of nitrate and bromide ion binding ability in DMSO. This sensitivity to geometrical changes and the affinity of 8 (X = O) to nitrate and bromide ions, which are poor hydrogen bond acceptors, confirm the predicted complementarity of ionophore binding site and anion geometry. According to DFT and MD calculations the higher affinity of 8 (X = O) to bromide than to nitrate is mainly due to the greater flexibility of the bromide complex and thus to its higher entropy. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002) Citing Literature Volume2002, Issue17September 2002Pages 3004-3014 RelatedInformation