Chemists are trained to recognize aromaticity semi-intuitively, using pictures of resonance structures and Frost-Musulin diagrams, or simple electron-counting rules such as Hückel's 4 + 2/4 rule. To quantify aromaticity one can use various aromaticity indices, each of which is a number reflecting some experimentally measured or calculated molecular property, or some feature of the molecular wavefunction, which often has no visual interpretation or may not have direct chemical relevance. We show that computed isotropic magnetic shielding isosurfaces and contour plots provide a feature-rich picture of aromaticity and chemical bonding which is both quantitative and easy-to-visualize and interpret. These isosurfaces and contour plots make good chemical sense as at atomic positions they are pinned to the nuclear shieldings which are experimentally measurable through chemical shifts. As examples we discuss the archetypal aromatic and antiaromatic molecules of benzene and square cyclobutadiene, followed by modern visual interpretations of Clar's aromatic sextet theory, the aromaticity of corannulene and heteroaromaticity.
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http://dx.doi.org/10.1039/d1cc03701c | DOI Listing |
Molecules
January 2025
Department of Materials Science and Engineering, University of Utah, Salt Lake City, UT 84112, USA.
Conducting polymers represent a crucial class of functional materials with widespread applications in diverse fields. Among these, poly(3,4-ethylenedioxythiophene) (PEDOT) and its derivatives have garnered significant attention due to their distinctive optical, electronic, and magnetic properties, as well as their exceptional tunability. These properties often exhibit intricate interdependencies, manifesting as synergistic, concomitant, or antagonistic relationships.
View Article and Find Full Text PDFMolecules
December 2024
Institute of Earth Sciences, Faculty of Natural Sciences, University of Silesia in Katowice, 60, Będzińska, 41-200 Sosnowiec, Poland.
Cathinone and its synthetic derivatives belong to organic compounds with narcotic properties. Their structural diversity and massive illegal use create the need to develop new analytical methods for their identification in different matrices. NMR spectroscopy is one of the most versatile methods for identifying the structure of organic substances.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Physics, University of Northeastern, IMIT-CONICET, Av. Libertad, 5500 Corrientes, Argentina.
In this study, we worked at the CCSD/aug-cc-pVTZ level to obtain the conformers of glycine in its neutral and zwitterionic forms in the gas and water phases. We then computed the NMR properties (spin-spin coupling constants and nuclear magnetic shieldings) at the SOPPA/aug-cc-pVTZ-J level. We attempt to elucidate the apparent discrepancy arising from two previous works by Valverde et al.
View Article and Find Full Text PDFSci Rep
January 2025
Department of Physics, Faculty of Science, Vali-e-Asr University of Rafsanjan, Rafsanjan, Iran.
To protect against harmful electromagnetic interference (EMI), it is crucial to fabricate composite with high total electromagnetic shielding efficiency (SE); In this study, FeNi-NiFeO-SiO nanoparticles (NPs) were synthesized using one-pot method and decorated on carbon nanotube's (CNT) sidewall. The final product was magnetic-ceramic/conductive (FeNi-NiFeO-SiO/MWCNT) nanocomposite. The EMI shielding characteristic of FeNi-NiFeO-SiO NPs and FeNi-NiFeO-SiO/MWCNT nanocomposite was investigated in the range of X and Ku frequency band.
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Research Unit of Structural Chemistry & Computational Biophysics, Leibniz-Forschungsinstitut für Molekulare Pharmakologie, Berlin 13125, Germany.
Density functional theory (DFT) calculations have emerged as a powerful theoretical toolbox for interpreting and analyzing the experimental nuclear magnetic resonance (NMR) spectra of chemical compounds. While DFT has been extensively used and benchmarked for isotropic NMR observables, the evaluation of the full chemical shielding tensor, which is necessary for interpreting residual chemical shift anisotropy (RCSA), has received much less attention, despite its recent applications in the structural elucidation of organic molecules. In this study, we present a comprehensive benchmark of carbon shielding anisotropies based on coupled cluster reference tensors taken from the NS372 benchmark data set.
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