Quantum mechanical study on complexation phenomenon of pillar[5]arene towards neutral dicyanobutane

ABSTRACT Based on density functional theory calculations, we have addressed the electronic structure, binding and nature of non-covalent interactions between alkylated pillar[5]arene (P[5]A) and 1,4-dicyanobutane (DCB)-based host-guest macrocycles. Neutral 1,4-dicyanobutane-based alkylated DCB_ProP[5]A is found to show higher binding energy when compared to the other three host-guest macrocycles. These complexes are largely stabilised by non-covalent interactions, which are ascertained through NCI and QTAIM analyses. Furthermore, the second-order perturbation energy of NBO analysis show that LP (N) – σ*(C-H) interactions predominate in DCB_ProP[5]A complex. Particularly, alkyl substituents (-methyl, -ethyl and -propyl) are playing a vital role in stabilising the host-guest complexes. In summary, the present work not only exhibits an efficient strategy to build a new family of alkylated P[5]A inclusion complexes but also providing deeper understanding on various non-covalent interactions towards 1,4-dicyanobutane (DCB) guest molecules inside the host environment. Graphical Abstract