Abstract
Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) with additional ab initio calculations were used to examine the alkali metal cation binding selectivity (i.e., molecular recognition) and host properties of tetraethyl resorcarene (1) and its per-methylated derivative (2). The significance of intramolecular hydrogen bonding for the crown conformation was demonstrated. The presence of intramolecular flip-flop hydrogen bonding in 1 was confirmed both with calculations and in ND3-exchange experiments. All the alkali metal cations formed host—guest complexes by docking inside the cavity of the host. Complexation with the larger cations, especially Cs+, was favored. All the alkali metal cations also formed dimeric resorcarene capsules with 1. The capsules were directly H-bonded species, with no linking solvent molecules. ND3-exchange experiments and molecular modeling revealed the significance of direct intermolecular H-bonding for the crown conformation of 1 and stability of the capsule structure.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Niederl, J. B.; Vogel, H. J. J. Am. Chem. Soc 1940, 62, 2512–2514 and references therein.
Högberg, A. G. S. J. Org. Chem 1980, 45, 4498–4500 and references therein.
Konishi, H.; Morikawa, O. Chem. Commun. 1993, 34–35.
Abis, L.; Dalcanale, E.; du Vosel, A.; Spera, S. J. Chem. Soc. Perkin Trans. II 1990, 2075–2080.
Adams, H.; Davis, F.; Stirling, C. J. M. Chem. Commun. 1994, 2527–2528.
Leigh, D. A.; Linnane, P.; Pritchard, R. G.; Jackson, G. Chem. Commun. 1994, 389–390.
Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397–5404.
Nissinen, M.; Wegelius, E.; Falábu, D.; Rissanen, K. Cryst. Eng. Comm. 2000, 28, 1–3 and references therein.
Tunstadt, L. M.; Tucker, J. A.; Dalcanale, E.; Weiser, J.; Bryant, J. A.; Sherman, J. C.; Helgersson, R. C.; Knobler, C. B.; Cram, D. J. J. Org. Chem. 1989, 54, 1305–1312.
Konishi, H.; Morikawa, O. Chem. Express 1991, 10, 801–804.
Schneider, H-J.; Güttes, D.; Schneider, U. J. Am. Chem. Soc. 1988, 110, 6449–6454.
Davis, F.; Stirling, J. M. Langmuir 1996, 12, 5356–5374.
Friggeri, A.; van Veggel, F. J. C. M.; Reinhoudt, D. N. Chem. Eur. J 1999, 5, 3595–3602.
Davis, F.; Lucke, A. J.; Smith, K. A.; Stirling, C. J. M. Langmuir 1998, 14, 4180–4185.
Sugiyama, K.; Esumi, K.; Koide, Y. Langmuir 1996, 12, 6006–6010.
Dutton, P. J.; Conte, L. Langmuir 1999, 15, 613–617.
Schneider, H.-J.; Schneider, U. J. Inclusion Phenom. Mol. Recog. 1994, 19, 67–83.
Fox, D.; Drew, M. G. B.; Wilkinson, E. S. J.; Beer, P. D. Chem. Commun. 2000, 391–392.
Cram, D. J.; Cram, J. M. Container Molecules and Their Guests. The Royal Society of Chemistry: Cambridge, 1994 Chap. V and references therein.
Ma, S.; Rudkevich, D. M.; Rebek, J.; Jr. J. Am. Chem. Soc. 1998, 120, 4977–4981.
Körner, S. K.; Tucci, F. C.; Rudkevich, D. M.; Heinz, T.; Rebek, J., Jr. Chem. Eur. J. 2000, 6, 187–195.
Conn, M. M.; Rebek, J., Jr. Chem. Rev. 1997, 98, 1647–1668.
Cho, Y. L.; Rudkevich, D. M.; Shivanyuk, A.; Rissanen, K.; Rebek, J., Jr. Chem. Eur. J. 2000, 6, 3788–3796.
Timmermann, P.; Verboom, W.; van Veggel, F. J. C. M.; Van Hoorn, D.; Reinhoudt, D. N. Angew. Chem. Intl. Ed. Engl. 1994, 33, 1292–1295.
Chopra, N.; Sherman, J. Angew. Chem. Intl. Ed. Engl. 1997, 36, 1727–1729.
Fox, D.; Drew, M. G. B.; Beer, P. D. Angew. Chem. Int. Ed. Engl. 2000, 39, 135–140.
Schalley, C. A.; Martín, T.; Obst, U.; Rebek, J., Jr. J. Am. Chem. Soc. 1999, 121, 2133–2138.
Schalley, C. A.; Castellano, R. K.; Brody, M. S.; Rudkevich, D. M.; Siuzdak, G.; Rebek, J., Jr. J. Am. Chem. Soc. 1999, 121, 4569–4579.
Schalley, C. A.; Rivera, J. M.; Martín, T.; Santamaria, J.; Siuzdak, G.; Rebek, J., Jr. Eur. J. Org. Chem. 1999, 1325–1331.
Schalley, C. A. Int. J. Mass Spectrom. 2000, 194, 11–39.
Ralph, S. F.; Iannitti, P.; Kanitz, R.; Sheil, M. M. Eur. Mass Spectrom. 1996, 2, 173–179.
Wang, K.; Gokel, G. W. J. Org. Chem. 1996, 61, 4693–4697.
Bartoszek, M.; Graubaum, H.; Wendland, D.; Dambovski, R. Eur. Mass Spectrom. 1999, 5, 81–88.
Shou, W. Z.; Browner, R. F. Anal. Chem. 1999, 71, 3365–3373.
Virelizier, A. H.; Moulin, C. M.; Jankowski, C. K.; Dozol, J. F.; Tabet, J. C. Spectroscopy 2000, 14, 127–139.
Leize, E.; Jaffrezic, A.; Van Dorssaeler, A. J. Mass. Spec. 1996, 31, 537–544.
de Koning, L. J.; Nibbering, N. M. M.; van Orden, S. L.; Laukien, F. J. Int. J. Mass Spectrom. Ion Processes 1997, 165/166, 209–219.
Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.9. Gaussian, Inc: Pittsburgh, 1998.
Kobayashi, K.; Asakawa, Y.; Kikuchi, Y.; Ayoama, Y. J. Am. Chem. Soc. 1993, 115, 2648–2654.
Gerkensmeier, T.; Iwanek, W.; Agena, C.; Fröhlich, R.; Kotila, S.; Näther, C.; Mattay, J. Eur. J. Org. Chem. 1999, 2257–2262.
Fukazawa, Y.; Deyama, K.; Usui, S. Tetrahedron Lett 1992, 33, 5803–5806.
Rose, K. N.; Barbour, L. J.; Orr, G. W.; Atwood, J. L. Chem. Commun. 1998, 407–408.
or]Shivanyuk, A.; Rissanen, K.; Kolehmainen, E. Chem. Commun. 2000, 1107–1108.
or]Murayama, K.; Aoki, K. Chem. Commun. 1998, 607–608.
Oshima, T.; Matsuda, F.; Fukushima, K.; Tamura, H.; Matsubayashi, G.; Arakawa, R. J. Chem. Soc. Perkin Trans. II 1998, 145–148.
Letzel, M. C. Agena C.; Mattay, J. Eur. J. Mass Spectrom. 2001, 7, 35–38.
Morrison, R. T.; Boyd, R. N. Organic Chemistry, 6th ed. Prentice Hall: Englewood Cliffs, 1992, pp 536–537.
Saenger, W.; Betzel, C.; Hingerty, B.; Brown, G. M. Nature 1982, 296, 581–583.
Rudkevich, D. M. Chem. Eur. J. 2000, 6, 2679–2686.
Tsue, H.; Ohmori, M.; Hirao, K. J. Org. Chem. 1998, 63, 4866–4867.
Saenger, W.; Betzel, C.; Hingerty, B.; Brown, G. M. Angew. Chem. Int. Ed. Engl. 1983, 22, 883–884.
Betzel, C.; Saenger, W.; Hingerty, B. E.; Brown, G. M. J. Am. Chem. Soc. 1984, 106, 7545–7557.
Chapman, R. G.; Sherman, J. C. Tetrahedron 1997, 53, 15911–15945.
Koide, Y.; Oka, T.; Imamura, A.; Shosenji, H.; Yamada, K. Bull. Chem. Soc. Jpn. 1993, 66, 2137–2142.
Grootenhuis, P. D. J.; Kollman, P. A.; Groenen, L. C.; Reinhoudt, D. N.; van Hummel, G. J.; Ugozzoli, F.; Andreetti, G. D. J. Am. Chem. Soc. 1990, 112, 4165–4176.
Thondorf, I. J. Chem. Soc. Perkin Trans. II 1999, 1791–1796.
Thondorf, I.; Brenn, J.; Böhmer, V. Tetrahedron 1998, 54, 12823–12828.
Timmermann, P.; Verboom, W.; Reinhoudt, D. N. Tetrahedron 1996, 52, 2663–2704.
Rudkevich, D. M.; Hilmersson, G. Rebek, J., Jr. J. Am. Chem. Soc. 1998, 120, 12216–12225.
Abis, L.; Dalcanale, E.; Duvosel, A.; Spera, S. J. Org. Chem. 1998, 53, 5475–5479.
Shivanyuk, A.; Paulus, E. F.; Böhmer, V. Angew. Chem. Int. Ed. 1999, 38, 2906–2909.
Harrison, A. G. Chemical Ionization Mass Spectrometry, 2nd ed. CRC Press: Boca Raton, 1992; p 171–174.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Mäkinen, M., Vainiotalo, P. & Rissanen, K. Alkali metal mediated resorcarene capsules: An ESI-FTICRMS study on gas-phase structure and cation binding of tetraethyl resorcarene and its per-methylated derivative. J Am Soc Mass Spectrom 13, 851–861 (2002). https://doi.org/10.1016/S1044-0305(02)00382-3
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1016/S1044-0305(02)00382-3