TY - JOUR
T1 - Hydrogen bonding in redox-modulated molecular recognition. An experimental and theoretical investigation
AU - Gray, Mark
AU - Cuello, Alejandro O.
AU - Cooke, Graeme
AU - Rotello, Vincent M.
PY - 2003/7/2
Y1 - 2003/7/2
N2 - Two receptors, a diaminotriazine derivative (DAT) and diamidopyridine (DAP), are complementary to the electroactive naphthalimide (N) 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 N. 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 Nred in the presence of DAT, with greater effects seen for the Nred·DAP 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.
AB - Two receptors, a diaminotriazine derivative (DAT) and diamidopyridine (DAP), are complementary to the electroactive naphthalimide (N) 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 N. 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 Nred in the presence of DAT, with greater effects seen for the Nred·DAP 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.
UR - http://www.scopus.com/inward/record.url?scp=0037864487&partnerID=8YFLogxK
U2 - 10.1021/ja035228b
DO - 10.1021/ja035228b
M3 - Article
SN - 0002-7863
VL - 125
SP - 7882
EP - 7888
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 26
ER -