Wydział Chemii

Beata Kizior

Jarosław J. Panek

Bartłomiej M. Szyja

Aneta Jezierska

2021

Symmetry

13

564/1-564/18

10.3390/sym13040564

Naukowa

Angielski

Artykuł

^{Intra- and inter-molecular interactions were studied in 2,3-dichloro-5,8-dihydroxy-1,4-
naphthoquinone and 1,4-dihydroxy-anthraquinone to shed more light on the molecular assembly
phenomena. The electronic ground and excited states features of the compounds were investigated
to find structure-property dependencies. The theoretical study was carried out on the basis of Density
Functional Theory (DFT), its Time-Dependent (TD-DFT)} extension, ^{and using Car–Parrinello
Molecular Dynamics (CPMD). In order to show how the environmental effects modulate the physicochemical
properties, the simulations were performed in vacuo, with the solvent reaction field (Polarizable
Continuum Model (PCM) and water as a solvent) and crystalline phase. The intramolecular
hydrogen bonds and the bridged proton dynamics were analyzed in detail. The aromatic rings and
electronic structure changes were estimated using the Harmonic Oscillator Model of Aromaticity
(HOMA) and Atoms in Molecules (AIM) theory. The Symmetry-Adapted Perturbation Theory
(SAPT) was employed for interaction energy decomposition in the studied dimers and trimers. It
was found that the presence of a polar solvent decreased the energy barrier for the bridged proton
transfer. However, it did not significantly affect the aromaticity and electronic structure. The SAPT
results showed that the mutual polarization of the monomers in the dimer was weak and that the
dispersion was responsible for most of the intermolecular attraction. The intermolecular hydrogen
bonds seem to be much weaker than the intramolecular bridges. The TD-DFT results confirmed that
the electronic excitations do not play any significant role in the intramolecular proton transfer. The
CPMD results indicated that the protons are very labile in the hydrogen bridges. Short proton transfer
and proton-sharing events were observed, and a correlation between them in the twin bridges was
noticed, especially for the first investigated compound.}

naphthoquinone, anthraquinone, DFT, HOMA, AIM, SAPT, TD-DFT, CPMDnaphthoquinone, CPMD

CC-BY

https://doi.org/10.3390/sym13040564

http://www.mdpi.com/journal/metals