10.1021/ja035228b.s001 Mark Gray Mark Gray Alejandro O. Cuello Alejandro O. Cuello Graeme Cooke Graeme Cooke Vincent M. Rotello Vincent M. Rotello Hydrogen Bonding in Redox-Modulated Molecular Recognition. An Experimental and Theoretical Investigation American Chemical Society 2003 anion forms electroactive naphthalimide receptor EPR experiments anion form diaminotriazine DAT DAP binding constants Hydrogen Bonding Theoretical Investigation Computational simulations association constants hydrogen bond polarizability UB 3LYP diamidopyridine 2003-06-10 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Hydrogen_Bonding_in_Redox-Modulated_Molecular_Recognition_An_Experimental_and_Theoretical_Investigation/3651183 Two receptors, a diaminotriazine derivative (<b>DAT</b>) and diamidopyridine (<b>DAP</b>), are complementary to the electroactive naphthalimide (<b>N</b>) through three-point hydrogen bonding. The association constants of the two receptors were evaluated for both the fully oxidized and the radical anion forms of <b>N</b>. In the oxidized state, the two receptors displayed identical binding constants. Diamidopyridine, however, lowers the reduction potential of naphthalimide to a far greater extent than does diaminotriazine, indicating a greater affinity for diamidopyridine by naphthalimide in the radical anion form. This behavior was mirrored by EPR experiments that showed small deviations from the hyperfine coupling pattern of <b>N</b><b><sub>red</sub></b> in the presence of <b>DAT</b>, with greater effects seen for the <b>N</b><b><sub>red</sub></b><b>ยท</b><b>DAP</b> complex. Computational simulations using the UB3LYP/6-311+G(d,p)//UHF/6-31G(d) hybrid gave theoretical hyperfine constants in good quantitative agreement with the experimental results. Using this correlation, we determined that electrostatics and hydrogen bond polarizability play key roles in controlling redox-modulated molecular recognition.