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Keywords = twisted acenes

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14 pages, 5433 KB  
Article
The Magnetic Properties of Fluorenyl and tert-Butyl-nitroxyl Acene-Based Derivatives: A Quantum Chemical Insight
by Alyona A. Starikova, Maxim G. Chegerev, Andrey G. Starikov and Vladimir I. Minkin
Chemistry 2024, 6(5), 816-829; https://doi.org/10.3390/chemistry6050049 - 23 Aug 2024
Cited by 2 | Viewed by 1790
Abstract
Acenes, as a class of polycyclic aromatic hydrocarbons, attract considerable attention due to their remarkable nonlinear optical and magnetic properties. The aim of this work was the elucidation of the capability of radical-substituted acene derivatives to undergo spin-state-switching rearrangements. For this purpose, a [...] Read more.
Acenes, as a class of polycyclic aromatic hydrocarbons, attract considerable attention due to their remarkable nonlinear optical and magnetic properties. The aim of this work was the elucidation of the capability of radical-substituted acene derivatives to undergo spin-state-switching rearrangements. For this purpose, a series of acene-based (anthracene, pentacene, heptacene) molecules bearing fluorenyl and tert-butyl-nitroxyl radicals were investigated through comprehensive quantum chemical modeling of their electronic structures, isomerization and magnetic properties. A possible mechanism of the transformation of the closed-shell folded isomer into the biradical twisted structure of the bis-fluorenyl anthracene has been ascertained by applying the procedure of searching for the Minimum Energy Crossing Point. The conditions favoring the occurrence of spin-state-switching in such classes of polycyclic aromatic hydrocarbon derivatives have been formulated. By varying the size of an acene core and the type of radical substituent, the compounds capable of changing their magnetic properties have been revealed. Considering the unique features of radical-bearing acene-based derivatives, the proposed molecules can be used as functional materials in photonics and electronics. Full article
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14 pages, 10738 KB  
Article
Effect of Chalcogenophenes on Chiroptical Activity of Twisted Tetracenes: Computational Analysis, Synthesis and Crystal Structure Thereof
by Gayathri Jothish Kumar, Benny Bogoslavsky, Sashi Debnath and Anjan Bedi
Molecules 2023, 28(13), 5074; https://doi.org/10.3390/molecules28135074 - 28 Jun 2023
Cited by 3 | Viewed by 2175
Abstract
The synthesis of multiply substituted acenes is still a relevant research problem, considering their applications and future potential. Here we present an elegant synthetic protocol to afford tetra-peri-substituted naphthalene and tetracene from their tetrahalo derivatives by a Pd(0)-catalyzed C-C cross-coupling method in a [...] Read more.
The synthesis of multiply substituted acenes is still a relevant research problem, considering their applications and future potential. Here we present an elegant synthetic protocol to afford tetra-peri-substituted naphthalene and tetracene from their tetrahalo derivatives by a Pd(0)-catalyzed C-C cross-coupling method in a single step. The newly synthesized tetracenes were characterized by NMR, HRMS, UV-vis spectrophotometry, and single-crystal X-ray diffraction (SCXRD). In addition, the first systematic computational study of the effect of chalcogenophenyl substitutions on the chiroptical properties of twistacenes was reported here. The gas phase computational studies using density functional theory (DFT) on a series of chalcogenophene-substituted tetracenes revealed that their chiroptical activity could be systematically increased via the atomistic tuning of peripheral substituents. Full article
(This article belongs to the Section Organic Chemistry)
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