The nature of the blue color in the iodine-starch reaction is still a matter of debate. Some textbooks still invoke charge-transfer bands within a chain of neutral I2 molecules inside the hydrophobic channel defined by the interior of the amylose helical structure. However, the consensus is that the interior of the helix is not altogether hydrophobic-and that a mixture of I2 molecules and iodide anions reside there and are responsible for the intense charge-transfer bands that yield the blue color of the "iodine-starch complex". Indeed, iodide is a prerequisite of the reaction. However, some debate still exists regarding the nature of the iodine-iodine units inside the amylose helix. Species such as I3-, I5-, I7- etc. have been invoked. Here, we report UV-vis titration data and computational simulations using density functional theory (DFT) for the iodine/iodide chains as well as semiempirical (AM1, PM3) calculations of the amylose-iodine/iodide complexes, that (1) confirm that iodide is a pre-requisite for blue color formation in the iodine-starch system, (2) propose the nature of the complex to involve alternating sets of I2 and Ix- units, and (3) identify the nature of the charge-transfer bands as involving transfer from the Ix- σ* orbitals (HOMO) to I2 σ* LUMO orbitals. The best candidate for the "blue complex", based on DFT geometry optimizations and TD-DFT spectral simulations, is an I2-I5-I2 unit, which is expected to occur in a repetitive manner inside the amylose helix.
Keywords: DFT; TD-DFT; UV-vis; amylose; iodide; iodine; starch.