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| - Origins of Cooperative Noncovalent Host−Guest Chemistry in Mixed Valence Complexes
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| - The electronic effects resulting from noncovalent host−guest interactions between calix[6]arene and a rutheniumdimer, [Ru3O(OAc)6(CO)(ppy)]2-μ-pz (ppy = 4-phenyl pyridine, pz = pyrazine), are presented. The noncovalentinteraction is between the calix[6]arene and the ppy ligands of the dimer. The dimer can bind 2 equiv ofcalix[6]arene. The complex [Ru3O(OAc)6(CO)(ppy)]2-μ-pz forms a highly stable mixed valence ion withstrong electronic coupling between the two Ru3 clusters. The strength of the electronic interaction is foundto be moderated by calix[6]arene binding. Addition of calix[6]arene to the mixed valence ion causes theelectronic coupling to decrease. The binding of calix[6]arene is found to be cooperative. The origins ofcooperative binding are developed in terms of the potential energy surfaces associated with the symmetricand asymmetric mixed valence ion. In particular, it is found that symmetry breaking (through the binding ofa single calix[6]arene) destabilizes the mixed valence state. Restoration of symmetry (through the binding ofa second calix[6]arene) increases the stability of the mixed valence ion and provides an additional drivingforce for the binding of the second calix[6]arene.
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