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Hydrogen‐Bonding Clusters Leading to Formation of Supramolecular Dimers of Metalloporphyrin Receptors: Modulation of Lewis Acidity by π‐π Interactions
Author(s) -
Nakash Moshe,
ClydeWatson Zöe,
Feeder Neil,
Teat Simon J.,
Sanders Jeremy K. M.
Publication year - 2000
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20000616)6:12<2112::aid-chem2112>3.0.co;2-w
Subject(s) - supramolecular chemistry , chemistry , dimer , hydrogen bond , stacking , molecule , crystal structure , crystallography , zinc , metal , lewis acids and bases , stereochemistry , organic chemistry , catalysis
Two remarkable crystal structures are reported of a cyclic receptor 1 , containing two metalloporphyrin units. The overall crystal structure of 1 provides the first direct evidence that π‐stacking between two metalloporphyrins reduces the Lewis acidity of the metal ion and thereby dramatically reduces the affinity of zinc for external ligands; this effect was previously suggested indirectly by solution state binding studies. In addition, crystallising 1 from a different combination of solvents and the ability of 1 to distort its structure leads to the remarkable observation of a supramolecular dimer of inter‐penetrating macrocycles, 4 , held together by clusters of hydrogen‐bonded methanol molecules.