Two-way effects between hydrogen bond and intramolecular resonance effect: an ab initio study on complexes of formamide and its derivatives with water.

Ab initio calculations up to MP2/aug-cc-pVTZ//MP2/cc-pVTZ level, including natural charge population and natural resonance theory analyses, have been carried out to study the two-way effects between hydrogen bond (H-bond) and the intramolecular resonance effect by using the H-bonded complexes of formamide ( FAO) and its derivatives ( FAXs, X represents the heavy atoms in the substituent groups, CH 2, NH, SiH 2, PH, and S) with water as models. Unlike NH 3 and NH 2CH 3 which prefer being H-bond acceptors ( HA) to form H-bond with water, the amino groups in the six monomers, because of the resonance effect, prefer being H-bond donors ( HD) rather HA. Six monomers can all form HD complexes with water, and only two ( FAC and FASi) with the weakest resonance effect are able to form HA complexes with water. The HD H-bond and resonance effect enhance each other (positive two-way effects) whereas the HA H-bond and resonance effect weaken each other (negative two-way effects). The H-bond energies in the six HD complexes are nearly linearly correlated with the weights of the dipolar resonance in Pauling's model and the N-C bond lengths; the correlation coefficients are 0.91 and 0.93, respectively. The positive two-way effects also happens in FAO-water complex, in which the FAO CO group serves as HA ( HA co ). Interestingly, when the HD and HA co H-bonds are present in FAO H-bond complex simultaneously, the enhancements are much more significant, and the energies of the two types of H-bonds are much larger than those when only one type of H-bond is present, reflecting the cooperative effects. By using the knowledge to the two-way effects, we computationally designed a molecule ( FAO- BH 3 ) to increase H-bond energy. Because of the oxygen lone pair donation to the empty pi orbital of BH 3, FAO- BH 3 has a much stronger resonance effect than FAO. As a result, the H-bond energy (-5.55 kcal/mol) in HD H 2O ... FAO- BH 3 complex is much greater than the -3.30 kcal/mol in the HD H 2O...FAO complex. The two-way effects can be rationalized as follows: the resonance effect leads to intramolecular charge shifts in the monomers which facilitate or prevent the charge donation or acceptation of their H-bond partners. Therefore, the H-bonds are strengthened or weakened. In reverse, the charge donations or acceptations of their H-bond partners facilitate or prevent the intramolecular charge shifts in the monomer moieties, which enhance or weaken the resonance effect. The understanding to the two-way effects may be helpful in drug design and refinement by modulating the H-bond strength and in building empirical H-bond models to study large biological molecules. The study supports Pauling's resonance model.