caa a22 4500 605510857 CHVBK 20210128100648.0 cr unu---uuuuu 210128e20150601xx s 000 0 eng 10.1007/s00894-015-2661-x doi (NATIONALLICENCE)springer-10.1007/s00894-015-2661-x Sequential metalation of benzene: electronic, bonding, magnetotropic and spectroscopic properties of coinage metalated benzenes studied by DFT [Elektronische Daten] [Athanassios Tsipis, Dimitrios Gkarbounis] A series of coinage metalated benzenes formulated as C6H6-nMn (M = Cu, Ag, Au, n = 1-5) were investigated by means of density functional theory (DFT) calculations. The structural, energetic, magnetotropic and spectroscopic properties of the coinage metalated benzenes were analyzed thoroughly and compared to the respective properties of the archetype aromatic benzene molecule. In contrast to the latter, the C6H6-nMn (M = Cu, Ag, Au, n = 1-5) molecules are predicted to be aromatic even in their excited triplet state. Excellent linear correlations between (I) the zz component of the nucleus independent chemical shift [NICSzz(1)] values and the total negative natural charge acquired by the carbocyclic ring, and (ii) the NICSzz(1) vs wavelength (λ) of the HOMO → LUMO transitions in the absorption spectra of the coinage metalated benzenes were established. The emission spectra of the coinage metalated benzenes were characterized by high Δ E ( S 0 − T 1 ) $$ \varDelta {E}_{\left({\mathrm{S}}_0-{\mathrm{T}}_1\right)} $$ values, particularly for the di-substituted — and p-isomers, with the highest Δ E ( S 0 − T 1 ) $$ \varDelta {E}_{\left({\mathrm{S}}_0-{\mathrm{T}}_1\right)} $$ value of 67kcalmol−1 calculated for the m-M6H4Au2 species. The bonding pattern of the coinage metalated benzenes was analyzed thoroughly by means of a multitude of electronic structure calculation methods [natural bond orbital (NBO), atoms-in-molecules (AIM), electron localization function (ELF), reduced density gradient (RDG) and Sign(λ 2(r))ρ(r) functions]. Our findings indicate whole classes of new coinage metalated benzenes (mono-, di-, tri-, four- and five-substituted) opening a new chemistry for the coinage metalated benzenes, indicating that their chemistry will be worthwhile studying both experimentally and theoretically in the future. Graphical Abstract The complete series of coinage metalated benzenes were investigated by density functional theory methods. The structural, energetic, bonding, magnetotropic and spectroscopic properties of the coinage metalated benzenes were analyzed thoroughly. In contrast to the archetype aromatic benzene molecule, the coinage metalated benzenes are predicted to be aromatic even in their excited triplet state. Springer-Verlag Berlin Heidelberg, 2015 Coinage metalated benzenes nationallicence Magnetotropicity nationallicence DFT nationallicence Cuprated benzenes nationallicence Argentated benzenes nationallicence Aurated benzenes nationallicence Tsipis Athanassios Department of Chemistry, Tsipis Laboratory of Inorganic and General Chemistry, University of Ioannina, 45110, Ioannina, Greece aut Gkarbounis Dimitrios Department of Chemistry, Tsipis Laboratory of Inorganic and General Chemistry, University of Ioannina, 45110, Ioannina, Greece aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/6(2015-06-01), 1-20 1610-2940 21:6<1 2015 21 894 https://doi.org/10.1007/s00894-015-2661-x text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2661-x text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Tsipis Athanassios Department of Chemistry, Tsipis Laboratory of Inorganic and General Chemistry, University of Ioannina, 45110, Ioannina, Greece aut NATIONALLICENCE 700 1- Gkarbounis Dimitrios Department of Chemistry, Tsipis Laboratory of Inorganic and General Chemistry, University of Ioannina, 45110, Ioannina, Greece aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/6(2015-06-01), 1-20 1610-2940 21:6<1 2015 21 894