DFT and TD-DFT investigation of calix[4]arene interactions with TFSI− ion

Abstract

Understanding the interactions of the calix[n]arene molecules with a variety of invited chemicals entities is getting very important. In this context, we have studied a new host-guest such as the interaction of the calix[4]arenes with the bis (trifluoromethylsulfonyl) imide TFSI− ion. The energy gap has decreased from 3.53 eV to 2.11 eV indicating the reliability of the electrochemical evaluation of HOMO and LUMO energy levels. In a predominant number of cases, we obtain the spatial accumulation of HOMO and LUMO at the interface of phenol groups. Then, according to the QNBO charge distribution of these host-guests interactions, we have demonstrated the direction of charge transfer between the CX[4] molecule and the TFSI− ion. More importantly, the non covalent interactions (NCI) have been investigated that the endo-cavity position of the TFSI-4 is the most stable position between all these host-guests. By using DFT quantum methods, we have identified as a suitable host for TFSI− which can be used in the electronic technology.

Possibility of Complexation of the Calix[4]Arene Molecule with the Polluting Gases: DFT and NCI-RDG Theory

“…The stable structures of the studied systems (CX [4] and CX[4]-gas) have been calculated with the DFT method by using the B3LYP [16,[19][20][21] coupled to the D3BJ (empirical Becke and Johnson damping dispersion corrections) in combination with the 6-31 + G(d) basis set, as implemented in GAUSSIAN 09 package [22] and the Gauss View [23] as a visual program. We have been calculated the binding energies of the CX[4]-gas take into account the Basis Set Superposition Error (BSSE) counterpoise (CP) correction energy of Boys and Bernardi [24].…”

“…Also, the cavity of the CX [4] molecule have attracted the researchers to test a new guest materials to be functional in the medical [10][11][12] or micro-biological field [13,14]. In literature, we have noted that there are some works which discuss the encapsulation of the CX [4] with gases molecules (CH 4 , NH 3 and C 2 H 2 ) [15][16][17][18]. In our work, we have studied the photo-physical properties of the CX [4] ).…”

Energy Band Gap Investigation using First Principle Simulation and Tauc Plot Method of Calixarene and Calixarene-Drug Inclusion Complexes

“…In this view, calixarene-based nanosensors have been reported to display significant responses towards various guest molecules such as cation (Supian et al, 2022), anion (Edwards et al, 2021), and neutral molecule (Fort & Scott, 2016) based on the optimized structural and geometrical factors (Panchal et al, 2020). Furthermore, calixarene can remarkably act as a receptor for trapping or encapsulating chemical entities (Gassoumi et al, 2019), forming hostguest complexes, which continuously increases the interest as a significant host molecule in many fields of supramolecular chemistry (Fahmy et al, 2020), particularly in drug delivery and drug sensor systems (Yuksel et al, 2021). (Español & Villamil, 2019) Calixarene is an ideal host molecule for various therapeutic guest drugs due to its unique architecture macromolecule composed of an upper rim with a para-substituent phenolic ring, a lower rim with a phenolic hydroxyl group, and a hydrophobic π electron-rich core cavity (Figure 2).…”

A theoretical study of the global and local electrophilicity, nucleophilicity, polarizability and QTAIM theory for calix[4]arene-gas interaction

“…The optimization of CX [4] and CX [4]-gas have been performed by the Density Functional Theory (DFT) method by using the global hybrid generalized gradient approximation B3LYP [15,18,19,20] coupled to the D3BJ (empirical Becke and Johnson damping dispersion corrections) in combination with the 6-31þG(d) basis set, as implemented in a Gaussian 09 package [21] and the GaussView [22] as a visual program. The binding energies have been calculated taking into account the Basis Set Superposition Error (BSSE) counterpoise correction (CP) according to the formalism of Boys and Bernardi [23].…”

“…The specific cavity of the CX [4] has attracted the experimenters and may be used in the medical [10,11,12] or micro-biological field [13,14]. In the literature, there are several works which discuss the interaction of CX [4] with small molecule (CH 4 ) and gas molecules (NH 3 and C 2 H 2 ) [5,15,16,17]. Herein, we have studied the physical and chemical properties of the CX [4]-NO 3 , CX [4]-NO 2 , CX [4]-N 2 and CX [4]-CO 2 complexes (The specific gas in the endo or exo-cavity position).…”