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Volumn 6, Issue 12, 2000, Pages 2112-2119

Hydrogen-bonding clusters leading to formation of supramolecular dimers of metalloporphyrin receptors: Modulation of Lewis acidity by π- π interactions

Author keywords

Hydrogen bonds; Metalloporphyrins; Pi interactions; Structure elucidation; Supramolecular chemistry

Indexed keywords

DIMER; MACROCYCLIC COMPOUND; METAL ION; METALLOPORPHYRIN; METHANOL; RECEPTOR; SOLVENT;

EID: 0034674289     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3765(20000616)6:12<2112::AID-CHEM2112>3.0.CO;2-W     Document Type: Article
Times cited : (36)

References (56)
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    • In some host systems, inclusion of solvent molecules and their displacement by a single ligand guest molecule was suggested as the main driving force for binding and acceleration of bimolecular reactions: a) J. Kang, J., Jr. Rebek, Nature 1996, 382, 239-241; b) J. Kang, J. Santamaria, G. Hilmersson, J. Jr. Rebek, J. Am. Chem. Soc. 1998, 120, 7389-7390.
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    • For other examples of chiral structures in crystals formed due to a twist see: a) D. G. Hamilton, J. E. Davies, L. Prodi, J. K. M. Sanders, Chem. Eur. J. 1998, 4, 608-620; b) R. G. Chapman, G. Olovsson, J. Trotter, J. C. Sherman, J. Am. Chem. Soc. 1998, 120, 6252-6260; c) J. R. Fraser, B. Borecka, J. Trotter, J. C. Sherman, J. Org. Chem. 1995, 60, 1207-1213; d) D. J. Cram, M. E. Tanner, C. B. Knobler, J. Am. Chem. Soc. 1991, 113, 7717-7727; e) D. O'Krongly, S. R. Denmeade, M. Y. Chiang, R. Breslow, J. Am. Chem. Soc. 1985, 107, 5544-5545.
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    • For other examples of chiral structures in crystals formed due to a twist see: a) D. G. Hamilton, J. E. Davies, L. Prodi, J. K. M. Sanders, Chem. Eur. J. 1998, 4, 608-620; b) R. G. Chapman, G. Olovsson, J. Trotter, J. C. Sherman, J. Am. Chem. Soc. 1998, 120, 6252-6260; c) J. R. Fraser, B. Borecka, J. Trotter, J. C. Sherman, J. Org. Chem. 1995, 60, 1207-1213; d) D. J. Cram, M. E. Tanner, C. B. Knobler, J. Am. Chem. Soc. 1991, 113, 7717-7727; e) D. O'Krongly, S. R. Denmeade, M. Y. Chiang, R. Breslow, J. Am. Chem. Soc. 1985, 107, 5544-5545.
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    • note
    • [10b]
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    • 4-plane) in the second porphyrin unit.
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    • In effect this is a manifestation of the cation-π interaction (D. A. Dougherty, Science 1996, 271, 163), with the nearby π system appearing to act as a weak fifth ligand for the Zn atom. The Zn-π distance is much greater than in a conventional Zn-O bond so it is not surprising that we detect no displacement of the metal from the porphyrin plane.
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    • The possible π-π interaction between porphyrins p2 and p3 in complex 4 (Figure 5) is probably weak (if it exists at all), given the geometrical relationship, and therefore it is not expected to significantly change the Lewis acidity of the Zn atoms.
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    • 4 planes in the various receptors should correspondingly be corrected.
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    • As the directional properties in hydrogen bonding of the O-H⋯O type are very soft (see: R. Taylor, O. Kennard, Acc. Chem. Res. 1984, 17, 320-326), this gives further confidence for hydrogen bonding in the framework drawn in Figure 6.
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    • As the precision in the location of hydrogen atoms is less than for oxygen atoms, we present the O⋯O distances. However, Figure 6 represents the observed relative orientation of the hydrogen bonding in complex 4.
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    • 4 plane in porphyrins p3 and p2, respectively.
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    • π-π interactions between coordinated pyridine ligands and between these ligands and a pyrrole unit of porphyrins, in a cyclic metalloporphyrin trimer, were believed to be the driving force for the formation of an interpenetrated dimer of trimers in the solid state: H. L. Anderson, A. Bashall, K. Henrick, M. McPartlin, J. K. M. Sanders, Angew. Chem. 1994, 106, 445-447; Angew. Chem. Int. Ed. Engl. 1994, 33, 429-431.
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    • π-π interactions between coordinated pyridine ligands and between these ligands and a pyrrole unit of porphyrins, in a cyclic metalloporphyrin trimer, were believed to be the driving force for the formation of an interpenetrated dimer of trimers in the solid state: H. L. Anderson, A. Bashall, K. Henrick, M. McPartlin, J. K. M. Sanders, Angew. Chem. 1994, 106, 445-447; Angew. Chem. Int. Ed. Engl. 1994, 33, 429-431.
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