Predicting Supramolecular Connectivity of Metal-Containing Solid-State Assemblies using Calculated Molecular Electrostatic Potential Surfaces

Abstract

We demonstrated that the primary supramolecular features of metal-based solid-state systems can be reliably predicted based solely on the relative strengths of competing hydrogen-bond acceptor sites. The predictive protocol utilizes a simple electrostatic view of the hydrogen bond and ranks the multiple acceptor sites according to calculated molecular electrostatic potential (MEP) surface values. The MEP was calculated for competing acceptors on 12 zero-dimensional (0-D) 2,4-pentanedionate (acac)-based complexes (Ni­(II), Co­(II), Cu­(II)), equipped with the lactam moiety, and the structural outcome was successfully predicted in 10 of 12 compounds by comparing the MEP difference between two acceptors, namely, the lactam and acac-based oxygen atoms. The two acceptor sites displayed structural selectivity as long as there was a substantial difference (ΔE > ΔE cutoff) between their relative hydrogen-bond acceptor capabilities. In the remaining two cases, the expected coordination geometry around the metal center did not materialize, which meant that a prediction of the supramolecular details could not be done. The working cutoff value (ΔE cutoff ≈ 30 kJ/mol) proved to be a valid and decisive criterion for predicting the supramolecular connectivity in these 0-D systems. The results further indicate that the ΔE cutoff is likely to be primarily dependent on the supramolecular functionality itself rather than on external “packing forces”.

Low-Dimensional Hybrid Indium/Antimony Halide Perovskites: Supramolecular Assembly and Electronic Properties

“…Analysis of the acceptor and donor characteristics of the In 2 X 10 4– and Sb 2 X 10 4– anions allows for a rationalization of the assembly motifs, the importance of which has been realized by ourselves and others. ,,− Thus, we present a detailed description of the isodensity surface-mapped electrostatic potentials (ESPs) of the dimeric In 2 X 10 4– and Sb 2 X 10 4– species observed herein (Figure ). The electrostatic potential is useful in identifying the relative distribution of electron density around the anionic and cationic building units.…”

“…Electrostatic potentials were generated on an electron density surface at 0.002 ε bohr –1 where areas of positive/negative potential indicate electron-rich/deficient regions. Electrostatic potentials generated at this isodensity value have been determined by previous studies to be an accurate indicator for supramolecular assembly …”

“…Electrostatic potentials generated at this isodensity value have been determined by previous studies to be an accurate indicator for supramolecular assembly. 78 Density of States (DOS) and Natural Bond Orbitals (NBOs). To determine the presence of hybridization and origin of UV−vis absorption, DFT-based density of state and natural bonding orbital calculations were performed on models of 1− 9.…”

Harnessing Bismuth Coordination Chemistry to Achieve Bright, Long-Lived Organic Phosphorescence

“…Electrostatic potentials were generated on an electron density surface at 0.002 ε/bohr where areas of positive/negative potential indicate electron-rich/deficient regions, respectively. Electrostatic potentials at this isodensity value have been determined by previous studies to be relevant in understanding the NCIs between ion pairs . Crystallographic building units of [HPhen] + and [Bi 2 (HPDC) 2 (PDC) 2 (NO 3 )] − were used as models for ESP calculations without further optimization.…”

Pyridine interaction with γ-CuI: synergy between molecular dynamics and molecular orbital approaches to molecule/surface interactions

“…Electrostatic potentials generated at this isodensity value have been determined by previous studies to be an accurate indicator for supramolecular assembly. 56,57 Natural bonding orbitals (NBO) and quantum theory of atoms in molecules (QTAIM) NBO calculations were performed using the NBO7 software suite utilizing the individual components constructed from the Molecular Dynamic outputs. NBO second order perturbation theory was applied to parse out the donor-acceptor interaction between the Py electron donor and the Cu or I electron acceptor including deconvoluting the sub-noncovalent interaction types, i.e.…”