Theoretical Modeling for Electronic Structure of Polyiodide Species Included in alpha-Cyclodextrin.

Molecular mechanism of the blue color formation in an iodine-starch reaction is studied by employing the iodine-alpha-cyclodextrin (alpha-CD) complex as a practical model system that resembles the structural properties of the blue amylose-iodine complex. To this end, we construct, using the quantum chemistry method, a molecular model of the complex (I5-/Li+/2alpha-CD) that consists of one I5-, two molecules of alpha-CD, and a lithium cation, and this model is employed as a basic unit in constructing structural models of polyiodide ion (I5-)n. The initial structure in the geometry optimization is adopted from the alpha-CD-iodine complex structure obtained from the X-ray crystallography study. The structural models of (I5-)n are built by adding the basic unit n times along the crystal axis and by optimizing the structure using quantum mechanics / molecular mechanics (QM (iodine) /MM (alpha-CD)) calculation. The electronic absorption spectra of the resulting model structures are calculated by time-dependent density functional theory (TD-DFT). We find that I5- acts as a basic unit of coloration in the visible region. The visible color originates from the electronic transition within the I5- molecule and any charge transfer between the I5- ion and either of alpha-CD or a coexisting counter cation are not involved. We also reveal that the electronic transitions of (I5-)n are delocalized, which accounts for the well-known observation that the color of the iodine-starch reaction becomes bluish with an increase in the chain length of amylose. Furthermore, pre-resonance Raman spectra calculated from the model suggest that the vibrational motions are localized in the I5- subunit dominantly. A comparison between an experimental absorption spectrum feature of alpha-CD-iodine complex and the calculated ones of (I5-)n ions with various n values suggests that (I5-)4 polyiodide ions tend to be populated dominantly in the alpha-CD-iodine complex under aqueous conditions.