Control of hydrogen bond strengths through push-pull effects triggered by a remote reaction center: a theoretical study.
In an effort to manipulate the bond strengths of hydrogen bonds, we have studied a three-component chemical system consisting of a reaction center, a conjugated bridge, and a hydrogen-bonding site. Protonation of the reaction center triggers intramolecular charge transfer from the hydrogen-bonding site, altering its affinity to bind to an acceptor. Previously, we had found that this communication (signal transduction) between the reaction center and the hydrogen-bonding site does not necessarily die out with increasing length of the conjugated bridge. In certain cases, this signal transduction is maintained-and even amplified-over long distances (I. Chao, T.-S. Hwang, Angew. Chem. 2001, 113, 2775-2777; Angew. Chem. Int. Ed. 2001, 40, 2703-2705). In this study we report the results of an extensive theoretical investigation of this problem to provide insights into this intriguing phenomenon. In the systems we investigated it was found that the push-pull process between the hydrogen-bonding site and the protonatable reaction center was mediated with the greatest facility by conjugated bridges with low-lying pi and pi* orbitals.
Hwang
Tsong-Song
TS
Institute of Chemistry, Academia Sinica, Taipei 11529, Taiwan.
Juan
Ning
N
Chen
Hsing-Yin
HY
Chen
Cheng-Chung
CC
Lo
Shih-Jung
SJ
Chao
Ito
I
D000641:Ammonia / Q000737:chemistry; D001665:Binding Sites; D006576:Heterocyclic Compounds, 4 or More Rings / Q000737:chemistry; D006860:Hydrogen Bonding; D008956:Models, Chemical; D008962:Models, Theoretical; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D011758:Pyrroles / Q000737:chemistry
D006576:Heterocyclic Compounds, 4 or More Rings; D009942:Organometallic Compounds; D011758:Pyrroles; D000641:Ammonia