Abstract
An organic supramolecular salt hydrate (imidazolium:N-phthalolylglycinate:H2O; IM+-NPG−-HYD) has been examined for its charge-transfer (CT) characteristics. Accordingly, IM+–NPG−–HYD has been characterized thoroughly using various spectroscopic techniques. Combined experimental and quantum chemical studies, along with wave function analysis, were performed to study the non-covalent interactions and their role in CT in the supramolecular salt hydrate. Notably, IM+–NPG−–HYD crystalizes in two configurations (A and B), both of which are held together via non-covalent interactions to result in a three-dimensional CT supramolecular assembly. The through-space CT occurs from NPG– (donor) to IM+ (acceptor), and this was mediated via non-covalent forces. We demonstrated the role of π–π stacking interactions (mixed-stacking donor-acceptor interactions) in the presence of charge-assisted hydrogen bonds in the regulation of CT properties in the self-assembly of the IM+–NPG−–HYD salt hydrate.
Highlights
The self-assembly characteristics of non-covalent interactions, such as hydrogen bonds, π–π stacking, and other weak van der Waals forces participating inchemical processes, have inspired supramolecular chemists to employ them effectively in crystal engineering [1,2]
Three factors could be responsible for the deviation in the computed spectrum: (1) the environmental factor as DFT calculations were performed with solvation effect while experimental data was obtained at solid-state; (2) the calculated frequencies are included only harmonic while experimental have both harmonic and anharmonic effect; and (3) basis set and DFT functional discrepancies
We have presented two-dimensional (2D) fingerprint plots for each observed interaction between the atom pairs in the salt hydrate
Summary
The self-assembly characteristics of non-covalent interactions, such as hydrogen bonds, π–π stacking, and other weak van der Waals forces participating in (bio)chemical processes, have inspired supramolecular chemists to employ them effectively in crystal engineering [1,2]. It hasbeen proven that different intermolecular interactions and/or crystal packing could highly modulate the optical and electronic properties of molecular crystals [5]. The formation of multi-component molecular materials (co-crystals, salts, and salt hydrates) has been extensively investigated with the development of crystal engineering or supramolecular chemistry [6–8]. Organic co-crystals, salts, and salt hydrates formed with different molecular moieties through intermolecular non-covalent interactions are attracting the attention of many researchers globally because of their applications in charge transport [9–11], photovoltaics [12], tunable light emitters [13,14], photoconductivity [15,16], ferroelectrics [17,18], nonlinear optics [19,20], light-driven actuators [21], and pharmaceuticals [22]. The dynamics of a proton or a hydrogen atom in the H-bonded
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
