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Flavin compounds are of great interest in biochemistry because of their diverse functions in catalytic and photochemical processes. The intrinsic optical properties of flavins depend sensitively on their environment such as complexation with metal ions. Herein, we characterize the interaction of alkali metal ions (M+) with riboflavin (RF, vitamin B2). To this end, two different experimental spectroscopic approaches are employed to determine the structural, vibrational, energetic, and optical properties of M+RF complexes by comparison wit