Simultaneous interactions of pyridine with substituted benzene ring and H–F in X-ben⊥pyr···H–F complexes: a cooperative study

Abstract

The cooperative effects between T-shape stacking and hydrogen bond interactions in X-ben\pyrÁÁÁH-F complexes were investigated in this work. The results indicate that the electron-withdrawing/donating substituents decrease/increase the magnitude of the binding energies compared to the unsubstituted X-ben\pyrÁÁÁH-F (X = H) complex. The cooperative effects have been studied while using the atoms in molecules (AIM) and natural bond orbital (NBO) methods, allowing us to evaluate the interplay between T-shape stacking and hydrogen bond interactions. There are good relationships among binding energies, Hammett constants, geometrical parameters, and the results of AIM and NBO analysis in X-ben\pyrÁÁÁH-F complexes.

Cooperativity in Noncovalent Interactions

“…Hydrogen bond operates in combination with numerous other noncovalent interactions (Figure ). A brief discussion on some of the studies exploring their coexistence and their mutual impact is given in the following section. − In this context, Geerlings and co-workers have investigated the interplay between aromatic stacking and hydrogen bonding in nucleobases by employing high-level quantum chemical calculations . Hydrogen-bonding capacity of the N3 and O2 atoms of cytosine was shown to increase linearly with the electrostatic repulsion between the stacked rings.…”

Stacking Interactions between 9-Methyladenine and Heterocycles Commonly Found in Pharmaceuticals

“…Stacking interactions are central to many areas of chemistry, including the binding of ligands to proteins and nucleic acids, − and harnessing such interactions lies at the heart of drug design. , In this context, understanding π-stacking interactions involving heterocycles is of paramount importance because heterocyclic fragments abound in drugs and bioactive natural products. − Model π-stacking interactions involving heterocycles have been studied both experimentally − and theoretically, , with the primary aim of unraveling the many factors that control their strength and preferred orientation. For instance, there have been numerous computational studies − of non-covalent interactions involving pyridine as a model N-heterocycle, building on the seminal work on the benzene–pyridine and pyridine–pyridine dimers by Hohenstein and Sherrill . Stacking interactions of other six-membered N-heterocycles (pyrimidine, triazine, tetrazine, etc.…”

The intricacies of the stacking interaction in a pyrrole–pyrrole system

“…Among NCI involving aromatic ring systems, the ones containing heteroaromatic rings have recently received greater attention [17][18][19][20][21][22]. Such rings are building blocks for anchoring substituents in defined positions and are a crucial component in most known drug molecules.…”