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.