Origins of cooperative noncovalent host-guest chemistry in mixed valence complexes

Benjamin James Lear, Clifford P. Kubiak

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Abstract

The electronic effects resulting from noncovalent host-guest interactions between calix[6]arene and a ruthenium dimer, [Ru3O(OAc) 6(CO)(ppy)2-μ-pz (ppy = 4-phenyl pyridine, pz = pyrazine), are presented. The noncovalent interaction is between the calix[6]arene and the ppy ligands of the dimer. The dimer can bind 2 equiv of calix[6]arene. The complex [Ru3O(OAc)6(CO)(ppy)] 2-μ-pz forms a highly stable mixed valence ion with strong electronic coupling between the two Ru3 clusters. The strength of the electronic interaction is found to be moderated by calix[6]arene binding. Addition of calix[6]arene to the mixed valence ion causes the electronic coupling to decrease. The binding of calix[6]arene is found to be cooperative. The origins of cooperative binding are developed in terms of the potential energy surfaces associated with the symmetric and asymmetric mixed valence ion. In particular, it is found that symmetry breaking (through the binding of a single calix[6]arene) destabilizes the mixed valence state. Restoration of symmetry (through the binding of a second calix[6]arene) increases the stability of the mixed valence ion and provides an additional driving force for the binding of the second calix[6]arene.

Original languageEnglish (US)
Pages (from-to)6766-6771
Number of pages6
JournalJournal of Physical Chemistry B
Volume111
Issue number24
DOIs
StatePublished - Jun 21 2007

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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