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Self‐Assembly, Characterisation, and Crystal Structure of Multinuclear Metal Complexes of the [2×3] and [3×3] Grid‐Type
Author(s) -
Breuning Esther,
Hanan Garry S.,
RomeroSalguero Francisco J.,
Garcia Ana M.,
Baxter Paul N. W.,
Lehn JeanMarie,
Wegelius Elina,
Rissanen Kari,
Nierengarten Hélène,
van Dorsselaer Alain
Publication year - 2002
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(20020802)8:15<3458::aid-chem3458>3.0.co;2-y
Subject(s) - chemistry , steric effects , ligand (biochemistry) , crystallography , crystal structure , counterion , metal , pyridine , protonation , stereochemistry , ion , medicinal chemistry , organic chemistry , biochemistry , receptor
The self‐assembly of new multimetallic complexes of grid‐type architecture is described. The binding of a set of tris‐terdentate ligands, 1 a – 1 d , based on terpyridine‐like subunits, with different octahedrally coordinated metal ions leads to the formation of species whose structure depends strongly on the ligand, the metal ion, the counterion, the solvent, and the reaction conditions. Under suitable conditions, the [3×3] grid was obtained from the reaction of ligand 1 a with zinc tetrafluoroborate and from ligand 1 b with mercury triflate. The other ligands led to the formation of mainly one compound of composition [M 6 L 5 ] 12+ , which has the structure of an incomplete [2×3] grid. The crystal structure of such a [2×3] grid, [Co 6 ( 1 d ) 5 ] 12+ , has been determined. In this complex, the three central pyrimidine—pyridine–pyrimidine non‐coordinating sites adopt transoid NCCN conformations. The much less stable cisoid conformations, the “pinching” of the coordination sites in the complex, the weaker donor strength of the central binding site, and the steric demand of the substituents are all factors contributing to the reluctance to produce the [3×3] structure. A subtle interplay between the nature of the metal, the steric demand of the ligand, the reaction conditions, and the type of counterion determine the product of self‐assembly. The results obtained show that by tuning the parameters, complexes containing six or nine octahedrally coordinated metal ions in a well‐defined grid‐type arrangement are accessible. Both types of arrays, [2×3] and [3×3], are of interest as self‐assembled inorganic architectures of well‐defined structure and nuclearity that may be suitable prototypes for selective information storage media.