Drawing small cations into highly charged porous nanocontainers reveals "water" assembly and related interaction problems

Angewandte Chemie - International Edition

Volumn 42, Issue 18, 2003, Pages 2085-2090

  Müller, Achim ^a   Krickemeyer, Erich ^a   Bögge, Hartmut ^a   Schmidtmann, Marc ^a   Botar, Bogdan ^a   Talismanova, Marina O ^a  

^a BIELEFELD UNIVERSITY   (Germany)

Author keywords

Cluster chemistry; Nanostructures; Polyoxometalates; Porous materials; Water

Indexed keywords

POROUS MATERIALS; POSITIVE IONS; SHELLS (STRUCTURES);

NANOCONTAINERS;

NANOSTRUCTURED MATERIALS;

NANOCAPSULE;

AQUEOUS SOLUTION; ARTICLE; GEOMETRY; MICROENCAPSULATION; MOLECULAR INTERACTION; MOLECULAR MODEL; NANOTECHNOLOGY;

EID: 0037687881     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200351126     Document Type: Article

References (44)

1. A. Müller, S. Sarkar, S. Q. N. Shah, H. Bögge, M. Schmidtmann, S. Sarkar, P. Kögerler, B. Hauptfleisch, A. X. Trautwein, V. Schünemann, Angew. Chem. 1999, 111, 3435; Angew. Chem. Int. Ed. 1999, 38, 3241.
2. A. Müller, S. Sarkar, S. Q. N. Shah, H. Bögge, M. Schmidtmann, S. Sarkar, P. Kögerler, B. Hauptfleisch, A. X. Trautwein, V. Schünemann, Angew. Chem. 1999, 111, 3435; Angew. Chem. Int. Ed. 1999, 38, 3241.
3. A. Müller, P. Kögerler, C. Kuhlmann, Chem. Commun. 1999, 1347-1358; L. Cronin, E. Diemann, A. Müller in Inorganic Experiments (Ed.: D. Woollins), Wiley-VCH, Weinheim, 2003, pp. 340-346.
4. A. Müller, P. Kögerler, C. Kuhlmann, Chem. Commun. 1999, 1347-1358; L. Cronin, E. Diemann, A. Müller in Inorganic Experiments (Ed.: D. Woollins), Wiley-VCH, Weinheim, 2003, pp. 340-346.
5. Water is highly structured but with random hydrogen-bonded links which results in medium-range regions disaggregating and reforming, a phenomenon generally described with so-called flickering clusters, which can be considered as a version of the i mixture-model of water (G. A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford University Press, New York, 1997). Femtosecond spectroscopy investigations support this picture (see S. Woutersen, U. Emmerichs, H. J. Bakker, Science 1997, 278, 658-660; see also S. W. Benson, E. D. Siebert, J. Am. Chem. Soc. 1992, 114, 4269-4276).
6. Water is highly structured but with random hydrogen-bonded links which results in medium-range regions disaggregating and reforming, a phenomenon generally described with so-called flickering clusters, which can be considered as a version of the i mixture-model of water (G. A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford University Press, New York, 1997). Femtosecond spectroscopy investigations support this picture (see S. Woutersen, U. Emmerichs, H. J. Bakker, Science 1997, 278, 658-660; see also S. W. Benson, E. D. Siebert, J. Am. Chem. Soc. 1992, 114, 4269-4276).
7. Water is highly structured but with random hydrogen-bonded links which results in medium-range regions disaggregating and reforming, a phenomenon generally described with so-called flickering clusters, which can be considered as a version of the i mixture-model of water (G. A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford University Press, New York, 1997). Femtosecond spectroscopy investigations support this picture (see S. Woutersen, U. Emmerichs, H. J. Bakker, Science 1997, 278, 658-660; see also S. W. Benson, E. D. Siebert, J. Am. Chem. Soc. 1992, 114, 4269-4276).
8. G. W. Robinson, S.-B. Zhu, S. Singh, M. W. Evans, Water in Biology, Chemistry and Physics, World Scientific, Singapore, 1996, and references therein; M. E Chaplin, Biophys. Chem. 1999, 83, 211-221, and references therein.
9. G. W. Robinson, S.-B. Zhu, S. Singh, M. W. Evans, Water in Biology, Chemistry and Physics, World Scientific, Singapore, 1996, and references therein; M. E Chaplin, Biophys. Chem. 1999, 83, 211-221, and references therein.
10. [4] and which are also abundant in discrete assemblies in some of the clusters presented here. Clathrate hydrates have been investigated from several scientific points of view, for example, for understanding of the basic principles of structural chemistry, and also for their industrial use (see Gas Hydrates: Challenges for the Future (Eds.: G. D. Holder, P. R. Bishnoi), Ann. N. Y. Acad. Sci. 2000, 912 and G. A. Jeffrey in Inclusion Compounds, Vol. 1 (Eds.: J. L. Atwood, J. E. D. Davies, D. D. MacNicol), Academic Press, New York, 1984, pp. 135-190.
11. [4] and which are also abundant in discrete assemblies in some of the clusters presented here. Clathrate hydrates have been investigated from several scientific points of view, for example, for understanding of the basic principles of structural chemistry, and also for their industrial use (see Gas Hydrates: Challenges for the Future (Eds.: G. D. Holder, P. R. Bishnoi), Ann. N. Y. Acad. Sci. 2000, 912 and G. A. Jeffrey in Inclusion Compounds, Vol. 1 (Eds.: J. L. Atwood, J. E. D. Davies, D. D. MacNicol), Academic Press, New York, 1984, pp. 135-190.
12. [4] and which are also abundant in discrete assemblies in some of the clusters presented here. Clathrate hydrates have been investigated from several scientific points of view, for example, for understanding of the basic principles of structural chemistry, and also for their industrial use (see Gas Hydrates: Challenges for the Future (Eds.: G. D. Holder, P. R. Bishnoi), Ann. N. Y. Acad. Sci. 2000, 912 and G. A. Jeffrey in Inclusion Compounds, Vol. 1 (Eds.: J. L. Atwood, J. E. D. Davies, D. D. MacNicol), Academic Press, New York, 1984, pp. 135-190.
13. Regarding some related aspects of porous materials see J. W. Steed, Science 2002, 298, 976-977.
14. A. Müller, E. Krickemeyer, H. Bögge, M. Schmidtmann, F. Peters, Angew. Chem. 1998, 110, 3567-3571; Angew. Chem. Int. Ed. 1998, 37, 3360-3363; A. Müller, S. K. Das, E. Krickemeyer, C. Kuhlmann, Inorg. Synth. 2004, 34, in press (Ed.: J. Shapley).
15. A. Müller, E. Krickemeyer, H. Bögge, M. Schmidtmann, F. Peters, Angew. Chem. 1998, 110, 3567-3571; Angew. Chem. Int. Ed. 1998, 37, 3360-3363; A. Müller, S. K. Das, E. Krickemeyer, C. Kuhlmann, Inorg. Synth. 2004, 34, in press (Ed.: J. Shapley).
16. A. Müller, E. Krickemeyer, H. Bögge, M. Schmidtmann, F. Peters, Angew. Chem. 1998, 110, 3567-3571; Angew. Chem. Int. Ed. 1998, 37, 3360-3363; A. Müller, S. K. Das, E. Krickemeyer, C. Kuhlmann, Inorg. Synth. 2004, 34, in press (Ed.: J. Shapley).
17. A. Müller, S. Q. N. Shah, H. Bögge, M. Schmidtmann, P. Kögerler, B. Hauptfleisch, S. Leiding, K. Wittler, Angew. Chem. 2000, 112, 1677-1679; Angew. Chem. Int. Ed. 2000, 39, 1614-1616.
18. A. Müller, S. Q. N. Shah, H. Bögge, M. Schmidtmann, P. Kögerler, B. Hauptfleisch, S. Leiding, K. Wittler, Angew. Chem. 2000, 112, 1677-1679; Angew. Chem. Int. Ed. 2000, 39, 1614-1616.
19. A. Müller, S. Polarz, S. K. Das, E. Krickemeyer, H. Bögge, M. Schmidtmann, B. Hauptfleisch, Angew. Chem. 1999, 111, 3439-3443; Angew. Chem. Int. Ed. 1999, 38, 3241-3245.
20. A. Müller, S. Polarz, S. K. Das, E. Krickemeyer, H. Bögge, M. Schmidtmann, B. Hauptfleisch, Angew. Chem. 1999, 111, 3439-3443; Angew. Chem. Int. Ed. 1999, 38, 3241-3245.
21. a) A. Müller, E. Krickemeyer, H. Bögge, M. Schmidtmann, S. Roy, A. Berkle, Angew. Chem. 2002, 114, 3756-3761; Angew. Chem. Int. Ed. 2002, 41, 3604-3609; see also b) A. Müller, H. Bögge, E. Diemann, Inorg. Chem. Commun. 2003, 6, 52-53.
22. a) A. Müller, E. Krickemeyer, H. Bögge, M. Schmidtmann, S. Roy, A. Berkle, Angew. Chem. 2002, 114, 3756-3761; Angew. Chem. Int. Ed. 2002, 41, 3604-3609; see also b) A. Müller, H. Bögge, E. Diemann, Inorg. Chem. Commun. 2003, 6, 52-53.
23. a) A. Müller, E. Krickemeyer, H. Bögge, M. Schmidtmann, S. Roy, A. Berkle, Angew. Chem. 2002, 114, 3756-3761; Angew. Chem. Int. Ed. 2002, 41, 3604-3609; see also b) A. Müller, H. Bögge, E. Diemann, Inorg. Chem. Commun. 2003, 6, 52-53.
24. Kα radiation, graphite monochromator; hemisphere data collection in ω at 0.3° scan width in three runs with 606, 435, and 230 frames (θ = 0, 88 and 180°) at a detector distance of 5.0 cm). For all structures empirical absorption corrections were performed using equivalent reflections with the program SADABS. The structures were solved with the program SHELXS-97 and refined using SHELXL-93. (SHELXS/L, SADABS from G. M. Sheldrick, University of Göttingen, Göttingen (Germany), 1993/97; structure graphics with DIAMOND 2.1 from K. Brandenburg, Crystal Impact GbR, 2001). Further details on the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen, Germany (fax: (+49) 7247-808-666; e-mail: crysdata@fiz-karlsruhe.de), on quoting the depository number CSD-412950 (1). Crystallographic data (excluding structure factors) for 3 and 4 have been deposited at the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-202399 (3) and CCDC-202400 (4). These data can be obtained free of charge via www.ccdc.cam. ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ccdc.cam.ac.uk).
25. I. D. Brown in Structure and Bonding in Crystals, Vol. II (Eds.: M. O'Keeffe, A. Navrotsky), Academic Press, New York, 1981, pp. 1-30.
26. A. Müller, P. Kögerler, A. Dress, Coord. Chem. Rev. 2001, 222, 193-218.
27. A. Müller, P. Kögerler, H. Bögge, Struct. Bonding (Berlin) 2000, 96, 203-236.
28. 2 in 5 (see formula).
29. + ions while the distance to the second shell is correspondingly larger;
30. b) A. Malecki, A. Bielanski, E. Diemann, A. Müller, to be published in connection with related studies on the release of encapsulated components.
31. + ion on the surface of the cage and a neutral water molecule in the cavity (A. Khan, Chem. Phys. Lett. 2001, 338, 201-207).
32. [19] This result means that a thermodynamically stable, icosahedral cage of water molecules can only be expected around the larger cations.
33. F. Sobott, A. Wattenberg, H.-D. Barth, B. Brutschy, Int. J. Mass Spectrom. 1999, 185-187, 271-279, and references therein.
34. 100 cluster with the central O atoms tetrahedrally coordinated (for a proposed separation into shells see Figure 6);
35. b) M. Henry, ChemPhysChem 2002, 3, 607-616.
36. m-: (icosahedron +) dodecahedron + icosahedron which has larger electron densities than in the other mentioned cases. This is caused by the presence of Mo atoms of an encapsulated disordered polyoxomolybdate "swimming in water" with an as yet unknown structure and corresponds to a new state of encapsulated inorganic ions.
37. + ions (A. Müller, A. Clapa, H. Bögge, M. Schmidtmann, unpublished results).
38. a) D. Voet, J. G. Voet, Biochemistry, 2nd ed., Wiley, New York, 1995;
39. b) T. E. Creighton, Proteins: Structures and Molecular Properties, 2nd ed., Freeman, New York, 1997, pp. 156, 263-264, 295-296.
40. [23]
41. a) A. Müller, E. Diemann, C. Kuhlmann, W. Eimer, C. Serain, T. Tak, A. Knöchel, P. K. Pranzas, Chem. Commun. 2001, 1928-1929;
42. b) T. Liu, S. K. Das, E. Diemann, A. W. M. Dress, A. Müller, unpublished results.
43. Soft Matter Physics (Eds.: M. Daoud, C. E. Williams), Springer, Berlin, 1999.
44. In this context it is important to realize that we have the remarkable situation of "charged water assemblies": The hydrophilic nanoobjects, for example, the anionic sphere and wheel-type species with their hydrophilic surfaces covered with H20 ligands, behave like charged water assemblies as their surface is covered with a strongly fixed water skin/hydration shell which has a well-defined structure.