Unexpected roles of guest polarizability and maximum hardness, and of host solvation in supramolecular inclusion complexes: A dual theoretical and experimental study

René Castro, Marcelo J. Berardi, Emilio Córdova, Mariluz Ochoa De Olza, Angel E. Kaifer, Jeffrey D. Evanseck

Research output: Contribution to journalArticlepeer-review

77 Scopus citations


The origin of differential binding affinity and structural recognition between the inclusion complexes of cyclobis(paraquat-p-phenylene), 14+, and 1,4-substituted phenyl or 4,4'-substituted biphenyl derivatives has been jointly determined by spectrometric techniques and ab initio and semiempirical molecular orbital methods. The unusual boxed geometry and tetracationic charge distribution in 14+ are key molecular features which produce strong intermolecular interactions with guest and solvent molecules. Solvation was addressed by including up to 12 acetonitrile molecules in the theoretical model, which realigned the predicted gas-phase supramolecular structures and energies into excellent agreement with experiment. The computed complexation enthalpies, ΔH(bind), from the semiempirical molecular orbital PM3 method are on average within 1 kcal/mol of the experimental free energy binding data collected from absorption spectroscopy in acetonitrile. In addition, the computed geometric penetration and positioning of 14+/benzidine and 14+/4,4'-biphenol complexes are consistent with that reported from NMR NOE data. The partitioning of self-consistent field complexation energies from both classical and quantum forces has been determined by using Morokuma's variational energy decomposition technique. It was determined that the primary basis for the molecular recognition between 1,4-substituted phenyl guests and 14+ is short-range stabilizing electrostatic forces complemented by small amounts of polarizability and charge-transfer. In contrast, the recognition force between 4,4'-substituted biphenyl guests and 14+ is dominated by polarizability with a small contribution from electrostatics. Therefore, the balance between molecular polarizability and electrostatics controls the differential binding affinity and structural recognition with 14+. For the first time, we report that individual molecular properties of substituted guests correlate with the binding energies of corresponding 14+ inclusion complexes. Direct correlations between the 14+ binding energies and the computed molecular polarizability, maximum hardness, softness, and electronegativity of the guest have been identified. It is now plausible to consider the design and construction of new supramolecular assemblies based upon a few select molecular properties of the constituent molecules.

Original languageEnglish (US)
Pages (from-to)10257-10268
Number of pages12
JournalJournal of the American Chemical Society
Issue number42
StatePublished - Oct 23 1996

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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