The intramolecular hydrogen bond as a unit of molecular electronics: Molecular switching controlled by overcrowded intramolecular three-centered hydrogen bond

The equilibrium geometry of the 2,5-bis-[2-(pyridin-2-yl)-vinyl]-1H-pyrrole calculated at the MP2/6-311++G(d,p) level of theory evidences the breaking of one of the components in the three-centered intramolecular hydrogen bond due to the steric strain. For this reason, the three-centered intramolecular hydrogen bonding turns out to be asymmetric interaction involving the major and minor components. However, the reversible switching between these components under an external impact is also possible. Two different stable states with unequal geometric and electronic structure are observed in the derivatives of the 2,5-bis-[2-(pyridin-2-yl)-vinyl]1H-pyrrole. These molecules represent novel molecular switches operating due to the pendulum-like transition between the nonequivalent two-centered components of the overcrowded three-centered intramolecular hydrogen bond. Implantation of hydrogen bond as a unit of the molecular scale device enhances potential of molecular electronics and could serve as a step towards the construction of artificial biological ensembles.