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CC BY-NC-ND 4.0 · Organic Materials 2022; 4(03): 61-72
DOI: 10.1055/a-1896-6890
Supramolecular Chemistry
Original Article

Selective Recognition of Ammonium over Potassium Ion with Acyclic Receptor Molecules Bearing 3,4,5-Trialkylpyrazolyl Groups

Felix Fuhrmann
a   Institut für Organische Chemie, Technische Universität Bergakademie Freiberg, Leipziger Strasse 29, 09599 Freiberg, Germany
,
Wilhelm Seichter
a   Institut für Organische Chemie, Technische Universität Bergakademie Freiberg, Leipziger Strasse 29, 09599 Freiberg, Germany
,
Monika Mazik 
a   Institut für Organische Chemie, Technische Universität Bergakademie Freiberg, Leipziger Strasse 29, 09599 Freiberg, Germany
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Abstract

Among the 1,3,5-trisubstituted 2,4,6-triethylbenzenes bearing pyrazolyl groups, the compounds with 3,5-dimethylpyrazolyl moieties were found to be effective receptors for ammonium ions (NH4 +). The current study investigated the extent to which the incorporation of an additional alkyl group in the 4-position of the pyrazole ring affects the binding properties of the new compounds. 1H NMR spectroscopic titrations and investigations using isothermal titration calorimetry revealed that this small structural variation leads to a significant increase in the binding strength towards NH4 + and also improves the binding preference for NH4 + over K+. In addition to the studies in solution, crystalline complexes of the new triethyl- and trimethylbenzene derivatives, bearing 3,4,5-trialkylpyrazolyl groups, with NH4 +PF6 − were obtained and analyzed in detail. It is noteworthy that two of the crystal structures discussed in this work are characterized by the presence of two types of ammonium complexes. Studies focusing on the development of new artificial ammonium receptors are motivated, among other things, by the need for more selective ammonium sensors than those based on the natural ionophore nonactin.

Key words

molecular recognition - ammonium receptors - selectivity - structure–binding activity relationships

Supporting Information



Publication History

Received: 08 June 2022

Accepted after revision: 06 July 2022

Accepted Manuscript online:
11 July 2022

Article published online:
11 August 2022

© 2022. The authors. This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes, or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)

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  • References

    • 1a Ingildsen P, Olsson G. Water Sci. Technol. 2002; 46: 139
      CrossrefPubMed
    • 1b Kaelin D, Rieger L, Eugster J, Rottermann K, Bänninger C, Siegrist H. Water Sci. Technol. 2008; 58: 629
      CrossrefPubMed
    • 1c König A, Bachmann TT, Metzger JW, Schmid RD. Appl. Microbiol. Biotechnol. 1999; 51: 112
      CrossrefPubMed
    • 1d Athavale R, Kokorite I, Dinkel C, Bakker E, Wehrli B, Crespo GA, Brand A. Anal. Chem. 2015; 87: 11990
      CrossrefPubMed
    • 1e Reichert J, Sellien W, Ache HJ. Freseniusʼ J. Anal. Chem. 1991; 339: 467
      CrossrefPubMed
    • 1f Winkler S, Rieger L, Saracevic E, Pressl A, Gruber G. Water Sci. Technol. 2004; 50: 105
      CrossrefPubMed
    • 2a Zhang W, Zhang J. PCT Int. Appl. WO2016/040048 A1, 2016
      PubMed
    • 2b Radomska A, Bodenszac E, Głab S, Koncki R. Talanta 2004; 64: 603
      CrossrefPubMed
    • 2c Magalhães JMCS, Machado AASC. Analyst 2002; 127: 1069
      CrossrefPubMed
    • 2d Wolfbeis OS, Li H. Biosens. Bioelectron. 1993; 8: 161
      CrossrefPubMed
    • 2e Kovács B, Nagy G, Dombi R, Tóth K. Bionsens. Bioelectron. 2003; 18: 111
      CrossrefPubMed
    • 2f Kawabata Y, Sugamoto H, Imasaka T. Anal. Chim. Acta 1993; 283: 689
      CrossrefPubMed
    • 4a Siswanta D, Hisamoto H, Tohma H, Yamamoto N, Suzuki K. Chem. Lett. 1994; 23: 945
      CrossrefPubMed
    • 4b Bühlmann P, Pretsch E, Bakker E. Chem. Rev. 1998; 98: 1593
      CrossrefPubMed
    • 5a Suzuki K, Siswanta D, Otsuka T, Amano T, Ikeda T, Hisamoto H, Yoshihara R, Ohba S. Anal. Chem. 2000; 72: 2200
      CrossrefPubMed
    • 5b Sasaki S, Amano T, Monma G, Otsuka T, Iwasawa N, Citterio D, Hisamoto H, Suzuki K. Anal. Chem. 2002; 74: 4845
      CrossrefPubMed
    • 5c Graf E, Kintzinger JP, Lehn JM, LeMoigne J. J. Am. Chem. Soc. 1982; 104: 1672
      CrossrefPubMed
    • 5d Kim H-S, Park HJ, Oh HJ, Koh YK, Choi J-H, Lee D-H, Cha GS, Nam H. Anal. Chem. 2000; 72: 4683
      CrossrefPubMed
    • 5e Rahman MA, Kwon N-H, Won M-S, Hyun M-H, Shim Y-B. Anal. Chem. 2004; 76: 3660
      CrossrefPubMed
    • 5f Jon SY, Kim J, Kim M, Park SH, Jeon WS, Heo J, Kim K. Angew. Chem. Int. Ed. 2001; 40: 2116
      CrossrefPubMed
    • 5g Campayo L, Pardo M, Cotillas A, Jaúregui O, Yunta MJ, Cano C, Gomez-Contreras F, Navarro P, Sanz AM. Tetrahedron 2004; 60: 979
      CrossrefPubMed
  • 6 Pazik A, Skwierawska A. Sens. Actuators, B 2014; 196: 370
    CrossrefPubMed
    • 7a Chin J, Walsdorff C, Stranix B, Oh J, Chung HJ, Park S-M, Kim K. Angew. Chem. Int. Ed. 1999; 38: 2756
      CrossrefPubMed
    • 7b Chin J, Oh J, Jon SY, Park SH, Walsdorff C, Stranix B, Ghoussoub A, Lee SJ, Chung HJ, Park S-M, Kim K. J. Am. Chem. Soc. 2002; 124: 5374
      CrossrefPubMed
    • 7c Koch N, Seichter W, Mazik M. CrystEngComm 2017; 19: 3817
      CrossrefPubMed
    • 7d Schulze MM, Koch N, Seichter W, Mazik M. Eur. J. Org. Chem. 2018; 2018: 4317
      CrossrefPubMed
    • 7e Jonah TM, Mathivathanan L, Morozov AN, Mebel AM, Raptis RG, Kavallieratos K. New J. Chem. 2017; 41: 14835
      CrossrefPubMed
    • 7f Rueda-Zubiaurre A, Herrero-García N, del Rosario Torres M, Fernández I, Osío Barcina J. Chem. Eur. J. 2012; 18: 16884
      CrossrefPubMed
    • 7g Ahn KH, Kim S-G, Jung J, Kim K-H, Kim J, Chin J, Kim K. Chem. Lett. 2000; 29: 170
      CrossrefPubMed
    • 7h Kim H-S, Kim D-H, Kim KS, Choi J-H, Choi H-J, Kim S-H, Shim JH, Cha GS, Nam H. Talanta 2007; 71: 1986
      CrossrefPubMed
    • 7i Kim H-S, Kim D-H, Kim KS, Choi H-J, Shim JH, Jeong IS, Cha GS, Nam H. J. Inclusion Phenom. Macrocyclic Chem. 2003; 46: 201
      CrossrefPubMed
    • 7j Oh KS, Lee C-W, Choi HS, Lee SJ, Kim KS. Org. Lett. 2000; 2: 2679
      CrossrefPubMed
    • 8a Koch N, Seichter W, Mazik M. Tetrahedron 2015; 71: 8965
      CrossrefPubMed
    • 8b Arunachalam M, Ahamed BN, Ghosh P. Org. Lett. 2010; 12: 2742
      CrossrefPubMed
  • 9 Fuhrmann F, Meier E, Seichter W, Mazik M. Acta Cryst. 2022; E78 DOI: 10.1107/S2056989022006867.
    CrossrefPubMed
  • 10 Hynes MJ. J. Chem. Soc., Dalton Trans. 1993; 311
    CrossrefPubMed
  • 11 Hübler C. Chem. – Methods 2022; e202200006 preprint DOI: 10.1002/cmtd.202200006.
    CrossrefPubMed
  • 14 Schulze M, Schwarzer A, Mazik M. CrystEngComm 2017; 19: 4003
    CrossrefPubMed
    • 15a Nishio M. Phys. Chem. Chem. Phys. 2011; 13: 13873
      CrossrefPubMed
    • 15b Nishio M, Umezawa Y, Honda K, Tsuboyama S, Suezawa H. CrystEngComm 2009; 11: 1757
      CrossrefPubMed
    • 15c Nishio M, Umezawa Y, Suezawa H, Tsuboyama S. The Importance of Pi-Interactions in Crystal Engineering: Frontiers in Crystal Engineering. Tiekink ERT, Zukerman-Schpector J. Hoboken: Wiley; 2012: 1
      Google Scholar
  • 16 Desiraju GR, Steiner T. The Weak Hydrogen Bond in Structural Chemistry and Biology. Oxford University Press; Oxford: 1999
    Google Scholar
  • 17 Spek AL. Acta Cryst. 2015; C71: 9
    PubMed
  • 18 Spek AL. Acta Cryst. 2009; D65: 148
    PubMed
  • 19 Grepioni F, Cojazzi G, Draper SM, Scully N, Braga D. Organometallics 1998; 17: 296
    CrossrefPubMed
    • 20a Dance I. Encyclopedia of Supramolecular Chemistry. Atwood JL, Steed JM. New York: Dekker; 2004: 1076
      CrossrefGoogle Scholar
    • 20b James SL. Encyclopedia of Supramolecular Chemistry. Atwood JL, Steed JM. New York: Dekker; 2004: 1093
      CrossrefGoogle Scholar
    • 20c Salonen LM, Ellermann M, Diederich F. Angew. Chem. Int. Ed. 2011; 50: 4808
      CrossrefPubMed
    • Angew. Chem. 2011; 123: 4908
      CrossrefPubMed
    • 21a Köhler L, Seichter W, Mazik M. Eur. J. Org. Chem. 2020; 2020: 7023
      CrossrefPubMed
    • 21b Köhler L, Hübler C, Seichter W, Mazik M. RSC Adv. 2021; 11: 22221
      CrossrefPubMed
  • 22 Koch N, Mazik M. Synthesis 2013; 45: 3341
    Article in Thieme ConnectPubMed
  • 23 Andree SNL, Sinha AS, Aakeröy CB. Molecules 2018; 23: 163
    CrossrefPubMed
  • 24 Hartshorn CM, Steel PJ. Aust. J. Chem. 1995; 48: 1587
    CrossrefPubMed
  • 25 Morin TJ, Wanniarachchi S, Gwengo C, Makura V, Tatlock HM, Lindeman SV, Bennett B, Long GJ, Grandjean F, Gardinier JR. Dalton Trans. 2011; 40: 8024
    CrossrefPubMed
  • 26 Hillier AC, Zhang XW, Maunder GH, Liu SY, Eberspacher TA, Metz MV, McDonald R, Domingos A, Marques N, Day VW, Sella A, Takats J. Inorg. Chem. 2001; 40: 5106
    CrossrefPubMed
  • 27 Ardizzoia GA, Brenna S, Durini S, Therrien B, Trentin I. Dalton Trans. 2013; 42: 12265
    CrossrefPubMed
  • 28 Stoe & Cie. X-AREA and X-RED. Darmstadt, Germany: STOE & Cie GmbH; 2009
    PubMedGoogle Scholar
  • 29 Sheldrick GM. Acta Cryst. 2015; A71: 3
    CrossrefPubMed
  • 30 Sheldrick GM. Acta Cryst. 2015; C71: 3
    CrossrefPubMed