<![CDATA[Rare sugars have garnered significant attention owing to their beneficial biological activities and their potential applications in sustainable materials, agriculture, and medicine. However, despite extensive crystallographic and hydrogen-bonding studies, the electronic factors governing their molecular stability and crystal packing are still not fully understood. In this study, the DV-Xα molecular orbital method was employed to systematically analyze intramolecular charge distribution in ketohexoses, comparing D-chiral and D,L-racemic forms. The results reveal a clear distinction between two types of electronic behavior: (i) electronically stable sites (C2 and C5), where charge variation remains minimal (typically < 1 %), and (ii) adaptive sites (C3, C4, and C6), where charge distribution exhibits significant responsiveness to molecular environment. This finding provides a new electronic-structure-based framework that explains how localized charge stability and flexibility cooperatively govern crystal packing and intermolecular interactions, particularly hydrogen bonding. Even subtle variations in charge (< 1 %) were found to be chemically meaningful, as they systematically influence interaction patterns across different ketohexoses. These insights go beyond conventional structural analyses by establishing a direct link between intramolecular electronic structure and macroscopic material behavior. The present approach offers a foundation for rational design and functionalization of rare sugars in applications such as crystal engineering, pharmaceuticals, and sustainable agrochemical materials.]]>
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