[reaction: see text] Surprisingly, the anti-aromatic paratropic ring current of the planar D(4)(h) transition state of 1,3,5,7-cyclooctatetraene (COT) survives almost all the way to the equilibrium tub-shaped D(2)(d) COT structure (plane-to-plane distance, d = 0.76 A); the current vanishes at ca. 80% of the geometric change and ca. 90% of the energy change from planar to tub geometry.
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http://dx.doi.org/10.1021/ol052822c | DOI Listing |
Chemistry
January 2025
Hunan Normal University, Chemistry, Yue Lu Qu Lushan Road 36, 410081, Changsha, CHINA.
In order to examine the effects of the fused heterole on the electronic properties of aromatic and antiaromatic smaragdyrins, 2,3-thiophene- and 2,3-indole-fused [20]smaragdyrins were synthesized by Suzuki-Miyaura coupling and subsequent oxidative fusion reaction, and were reduced with NaBH4 to the corresponding [22]smaragdyrins. Fused-thiophene- and fused-pyrrole-bridged [20]- and [22]smaragdyrin dimers were also synthesized in the similar manner. The installed fused heteroles mitigate the paratropic ring current of the [20]smaragdyrin but exert only minor effects on the diatropic ring current of the [22]smaragdyrin.
View Article and Find Full Text PDFChemphyschem
January 2025
The University of Sheffield, school of mathematical and physical sciences, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
Pentalene (C8H6) and NN- and BB-bridged heterocyclic analogues (BN)4H6, derived by replacement of CC pairs with BN, are taken as paradigms for tuning of ring-current (anti)aromaticity by variation of π charge, electronegativity and substitution pattern. Ab initio calculation of maps for the π current density induced in these model systems by a perpendicular external magnetic field exhibits the full range of tropicity, from diatropic aromatic to nonaromatic to paratropic antiaromatic, with a ready rationalisation in terms of an orbital model. Further calculations on systems of varying charge in which these motifs are embedded in extended PAH systems with naphthalene and phenanthrene 'clamps' show promise for switching between current patterns and related opto-electronic properties.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry, Faculty of Science, University of Helsinki, P.O. Box 55, A. I. Virtasen aukio 1, Helsinki FIN-00014, Finland.
We have calculated the magnetically induced current density (MICD) susceptibility at the all-electron density functional theory level for a series of coronoid molecules of increasing size and compared the MICD susceptibilities with those calculated using the pseudo-π (PP) model. The molecules sustain global diatropic magnetically induced ring currents (MIRCs), whereas paratropic MICD vortices mainly appear inside the benzene rings. The computationally cheaper PP calculations were also employed on circum[]coronene molecules showing that the MICD pattern continues to alternate for odd and even when increasing the size of the molecule.
View Article and Find Full Text PDFChemistry
December 2024
Department of Chemistry, Faculty of Science, Niigata University, Nishi-ku, Niigata, 950-2181, Japan.
Porphyrinoids in the 20π-electron state have been extensively studied from the fundamental viewpoint of investigating their structure-antiaromaticity relationships. However, most of the 20π porphyrinoids are highly distorted and unstable in air, which hinder the comprehensive analysis of paratropic ring-current effects derived from planar π-electron systems. Herein, we present the first examples of antiaromatic Sn(IV) complexes of 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids (SnXTADAPs), prepared by the complexation of the corresponding freebases with Sn(II) chloride under aerobic conditions and subsequent metathesis of the axial ligands, that show paratropic ring-current effects.
View Article and Find Full Text PDFPhys Chem Chem Phys
October 2024
Research School of Chemistry and Applied Biomedical Sciences, National Research Tomsk Polytechnic University, Tomsk 634050, Russian Federation.
Magnetically induced ring-currents and magnetic susceptibilities have been calculated for the series of biphenylene sheets and biphenylene nanoribbons with armchair and zigzag edges with hydrogen atoms, as well as with bromine and fluorine atoms. Calculations have been performed at the density functional level of theory. It has been shown that biphenylene sheets and nanoribbons are characterized by dominant paratropic ring current, resulting in antiaromatic character.
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