Structure, electronic, inclusion complex formation behavior and spectral properties of pillarplex

Abstract

systems. The low binding energy, and the physical adsorption of guest molecule and HOMO-LUMO spatial diagram indicates, that the Au and Ag-Pillarplex can be used as reversible host for linear alkanes Complexation of guest engenders frequency shift in the vibrational spectra. Calculated 1 H NMR reveal that guest protons which are closer to the metal sites experience larger shielding possibly due to C-H→LP* metal interaction. The 15 N signal observed for the DAO is nearly identical to that observed for the DAO@ metal-Pillarplex. NBO and AIM analysis indicate that metal centers in host, play a major role in stabilizing the guest inside the cavity than the amino group on the guest molecule.Abstract Electronic structure, vibrational and NMR spectra of metal-Pillarplex (metal = Cu, Ag and Au) and its inclusion complex with 1,8-diaminooctane (DAO) are investigated by using density functional theory. The coordinated metal atoms tune the cavity size and the height of metal-Pillarplex and form a rigid cavity thereby reducing their structural deformation. Cu-Pillarplex undergoes a large deformation both on the host and guest molecule. The calculated Gibbs free energy for the formation of inclusion complex were negative indicating their facile formation at the room temperature. Computed binding energies with various functionals and energy decomposition analysis, shows that dispersion correction is essential in these Electronic supplementary material The online version of this article (

Sustainable Metallocavitand for Flue Gas-Selective Sorption: A Multiscale Study

“…68−70 To shed light on host capability of PPX, our group has already studied the electronic structure and the inclusion complex formation behavior of Ag, Au, and Cu metal-centered PPX with the linear chain 1,8-diaminooctane and found that the guest molecule binds ideally within the cavity. 71 Herein, we have explored various gas molecules, such as flue gas, biogas, syngas, corrosive gas, exhaust gas, greenhouse gas, etc. within the Au-PPX cavity and their adsorption and separation behaviors have been studied using multiscale modeling method.…”