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Metallosupramolecular Zippers Generated by Self‐Organization of Self‐Complementary Molecular Clefts
Author(s) -
Barboiu Mihail,
Petit Eddy,
Vaughan Gavin
Publication year - 2004
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/chem.200305750
Subject(s) - terpyridine , zipper , stacking , ligand (biochemistry) , chemistry , pyridine , crystallography , metal , stereochemistry , computer science , organic chemistry , receptor , biochemistry , algorithm
The binding of Co 2+ and Pb 2+ ions to the terpyridine and pyridine subunits of the ligand 1 leads to the self‐complementary molecular clefts 2 – 6 , which result from the crossover combination of orthogonal‐terpyridine and linear‐pyridine metal‐coordination subprograms and are stabilized by strong π–π stacking interactions. Four different cleft‐type entities, [Co 2+ 2 ( 1 ) 2 ] ( 3 ), [Pb 2+ 2 ( 1 ) 2 ] ( 4 ), [Co 2+ 4 ( 1 ) 2 ] ( 5) , [Pb 2+ 4 ( 1 ) 2 ] ( 6 ), are generated in both solution and the solid state, and may be interconverted as a function of metal/ligand stoichiometry. One‐ and two‐dimensional metallosupramolecular zipper architectures result from self‐assembly in the solid state driven by a combination of different π–π stacking subprograms. The U‐shaped geometry of the ligand influences the possibility of zipping and thus, in turn, the generation of different zipper architectures. The structures of 2 – 5 have been confirmed by X‐ray crystallography; that of 6 is based on NMR spectral data.