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Two Cu 21 Clusters with Pseudo‐ D 3 Symmetry Derived from the D ‐Saccharate Pentaanion, C 6 H 5 O 8 5−
Author(s) -
Abrahams Brendan F.,
McCormick Laura J.,
Moubaraki Boujemaa,
Murray Keith S.,
Robson Richard,
Waters Tom
Publication year - 2011
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.201100451
Subject(s) - orthorhombic crystal system , crystallography , chemistry , antiferromagnetism , cluster (spacecraft) , ion , ground state , crystal structure , atomic physics , physics , condensed matter physics , organic chemistry , computer science , programming language
The combination of Cu(NO 3 ) 2 , potassium hydrogen saccharate (KC 6 H 9 O 8 ) and 1,10‐phenanthroline (phen) yields a pair of chiral cluster compounds, each with composition Cu 21 (C 6 H 5 O 8 ) 6 (phen) 12 (NO 3 ) 12 ⋅solvate. One of the compounds forms as orthorhombic crystals, while the other forms cubic crystals. Each of the clusters has D 3 or approximate D 3 symmetry, but the arrangement of the saccharate ion in the clusters is quite different in the two cases. The clusters in the cubic form interact with neighbouring clusters through face‐to‐face π interactions involving the phen ligands, an association that leads to the generation of very large solvent‐filled spaces in the crystal structure. In contrast the clusters in the orthorhombic form are much more densely packed. At the centre of each cluster that crystallises in the orthorhombic form is a nitrate anion that binds to six Cu II centres. ESI mass spectral studies indicate that the Cu 21 clusters exist in solution. Solid‐state magnetic studies of the cubic form of Cu 21 show that antiferromagnetic coupling occurs to leave a non‐zero‐spin ground state, and comparisons are made to the magnetic data for other large Cu II clusters.