Tuning of the anion–π interaction

Abstract

In this manuscript, we report an ab initio theoretical study (RI-MP2/aug-cc-pVDZ) that deals with the effect of having different electron acceptor molecules interacting with the aromatic moiety (s-triazine) on the anion-p interaction strength. Depending on the type and number of interacting molecules, a wide range of complexation energies can be obtained, and therefore, a tuning of the interaction strength can be adjusted. In addition, cooperativity effects between the anion-p and a variety of other noncovalent and convalent interactions are analyzed and compared. We have used Bader's theory of ''atoms-inmolecules'' to demonstrate that the electron density computed at the bond critical point that emerges upon complexation can be used not only as a measure of bond order but also as a measure of cooperativity and interplay between the noncovalent interactions that coexist in the same complex.

Anion-π Interactions in Supramolecular Chemistry and Catalysis

“…16.3a) and s-triazine ( Fig. 16.3b) to Ag I dramatically enhances their ability to establish anion-π binding [83,85].…”

“…However, there is a limitation for the Fig. 16.3 Interaction energies of pyrazine a and triazine b anion-π complexes from references [84,85] first condition due to the reduced number of strong electron withdrawing groups available for constructing the binding blocks. To have a large value of Q zz , the use of -NO 2 and -CN groups is required.…”

Construction of Supramolecular Assemblies Based on Anion–π Interactions

“…Therefore, it is clear that in order to design an efficient anion receptor based on the anion-π interaction, the π-binding units should have a large and positive quadru pole moment and a large molecular polarizability. 11.2b) to Ag I dramatically enhances their ability to establish anion-π binding [77,81]. To have a large value of Q zz , the use of ─NO 2 and ─CN groups is required.…”

Triel–hydride triel bond between ZX3 (Z = B and Al; X = H and Me) and THMe3 (T = Si, Ge and Sn)

“…Besides the lone‐pair electrons, π‐electrons in aromatic or unsaturated molecules and the single electron in radicals are also taken as Lewis bases in triel bonding. When BX 3 (X = F, Cl, Br and I) compounds bind with π‐systems including ethene, 1,2‐difluoroethene and perfluoroethene, lone pair–π, halogen and triel bonding interactions are established, but triel bonding is the most favorable among the three types of interactions . Similarly, BH 2 X (X = F, Cl, Br and I) can participate in hydrogen, halogen and triel bonds in its homodimeric systems owing to its dual σ‐ and π‐hole nature .…”