Flavins are a diverse set of compounds with a wide variety of biological and nonbiological applications. Applications of flavins receiving attention recently consist of electro- and photocatalytic oxidation of substrates for organic synthesis, bioengineered nanotechnology, and water splitting catalysts, among others. While there is vast knowledge regarding the structure–property relationships of flavins and their electrochemistry, there is much less work elucidating the structure property relationships as they pertain to flavinium photochemistry. Herein, we report the effect of molecular tailoring on the molecular properties of N(5)-ethyl-flavinium cation (Et-Fl+), a derivative of the biocatalytic coenzyme riboflavin, by incorporating electron withdrawing and donating groups at the C7 and C8 position of the isoalloxazine ring. The presence of electron withdrawing groups at the C8 position caused a red shift in the absorption spectrum, while the electron donating groups caused a blue shift. Functionalization at the C7 position had the opposite effect on the absorption spectrum. The effects of single substitution were relatively negated with simultaneous functionalization at both the C8 and C7 positions. Difference density plots indicate no change in the nature of the S1 excited state, which was confirmed by optimization of the excited state geometries. The results presented in this study indicate that functionalization of the isoalloxazine unit affects the photophysical properties of N(5)-ethyl-flavinium cations.

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Alloxan is an important toxic glucose analogue used to induce diabetes in lab test animals. Once regarded as a "problem structure," the condensed-phase structure of anhydrous alloxan has largely been settled, but literature inconsistencies remain for the structure of the typically employed reagent alloxan monohydrate. Due to the criticality of structure−function relationships, we have used 1 H/ 13 C{ 1 H} NMR, IR spectroscopy, as well as quantum mechanical (QM) calculations to probe the liquid-phase structure and reactivity of alloxan monohydrate. In protic solvents (D 2 O and acetic acid-d 4 ), hydration at the C5 carbonyl of alloxan monohydrate occurs quantitatively to form the C5 gem-diol (5,5′-dihydroxybarbituric acid). In the aprotic solvent dimethyl sulfoxide (DMSO)-d 6 , there exists a mixture of the C5 gem-diol and planar tetraketo form of alloxan monohydrate. QM calculations explain the solvent-dependent hydration reactivity, where a solvent-assisted H-atom transfer mechanism lowers the activation energy of water addition at the C5 carbonyl by ∼16 or 27 kcal/ mol in water or acetic acid, respectively, compared to the unassisted hydration reaction. Prompt recrystallization of alloxan monohydrate from boiling water does not alter the structure of the reagent. These findings probe the exact structure of alloxan monohydrate to guide future research efforts in biological sciences and in organic synthesis.