Fulvalene Derivatives Containing a Tetrabenzofluorene Unit: New Nonplanar Fulvalenes with High Electron Affinity

Yamada, Kenta; Shibamoto, Hiroshi; Tanigawa, Yusuke; Ishikawa, Hiroyuki; Nishida, Jun‐ichi; Kitamura, Chitoshi; Kurata, Hiroyuki; Kawase, Takeshi

doi:10.1055/s-0035-1561478

Cited by 4 publications

(3 citation statements)

References 11 publications

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“…The studied 9,9’-BF based compounds were strategically designed and should exhibit interesting electrochemical properties (vide infra). Although the synthesis and some properties of 3 have been reported 29 , the structure was confirmed for the first time in this study using X-ray crystallography. Importantly, we found that the configurations of two semi-rigid helical substructures significantly affect the structural parameters and properties, which are discussed in the following sections.…”

Section: Introductionmentioning

confidence: 52%

Synthesis, structural analysis, and properties of highly twisted alkenes 13,13’-bis(dibenzo[a,i]fluorenylidene) and its derivatives

Kang,

Liu,

Shao

et al. 2023

Nat Commun

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The rotation of a C = C bond in an alkene can be efficiently accelerated by creating the high-strain ground state and stabilizing the transition state of the process. Herein, the synthesis, structures, and properties of several highly twisted alkenes are comprehensively explored. A facile and practical synthetic approach to target molecules is developed. The twist angles and lengths of the central C = C bonds in these molecules are 36–58° and 1.40–1.43 Å, respectively, and confirmed by X-ray crystallography and DFT calculations. A quasi-planar molecular half with the π-extended substituents delivers a shallow rotational barrier (down to 2.35 kcal/mol), indicating that the rotation of the C = C bond is as facile as that of the aryl-aryl bond in 2-flourobiphenyl. Other versatile and unique properties of the studied compounds include a broad photoabsorption range (from 250 up to 1100 nm), a reduced HOMO-LUMO gap (1.26–1.68 eV), and a small singlet-triplet energy gap (3.65–5.68 kcal/mol).

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Section: Introductionmentioning

confidence: 52%

Synthesis, structural analysis, and properties of highly twisted alkenes 13,13’-bis(dibenzo[a,i]fluorenylidene) and its derivatives

Kang,

Liu,

Shao

et al. 2023

Nat Commun

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show abstract

“…Moreover, its alkyl and phenylated derivatives have shown interesting fluorescence attributes in solution and in solid films [20] . Lastly, its fulvalene derivative and oxo forms performed well as electron acceptors [21] . In general, the synthesis of tetrabenzofluorene and its derivatives involves multiple synthetic steps [15–19,22] .…”

Section: Introductionmentioning

confidence: 99%

“…[20] Lastly, its fulvalene derivative and oxo forms performed well as electron acceptors. [21] In general, the synthesis of tetrabenzofluorene and its derivatives involves multiple synthetic steps. [15][16][17][18][19]22] In contrast, Dyker and co-workers demonstrated an efficient route to fluoreno [5]helicenes in one step by the solution-phase cyclodehydrogenation of pentaarylcyclopentadiene precursor (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Mechanochemical Scholl Reaction on Phenylated Cyclopentadiene Core: One‐Step Synthesis of Fluoreno[5]helicenes

Báti,

Csókás,

Stuparu

2023

Chemistry A European J

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In this study, we explore feasibility of the mechanochemical approach in the synthesis of tetrabenzofluorenes (fluoreno[5]helicenes). For this, commercially available phenylated cyclopentadiene precursors are subjected to the Scholl reaction in the solid state using FeCl3 as an oxidant and sodium chloride as the solid reaction medium. This ball milling process gave access to the 5‐membered ring containing‐helicenes in one synthetic step in high (95‐96%) isolated yields. The solution‐phase reactions, however, were found to be moderate to low yielding in this regard (10‐40%).

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On the Shape and Synthesis of Extended Fluorenones: Recent Advances and Upcoming Challenges

Large

Prim

2021

Eur J Org Chem

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Extended fluorenones represent a particular class of polycyclic compounds. The extension of the aromatic system through the fusion of additional benzene rings onto the central tricyclic fluorenone gives rise to an impressive topological diversity and allows to modulate the properties of the original molecule. The multiple ways this aromatic extension can be joined onto the tricyclic core generates multiple spatial arrangements from linear, angular, mixed linear-angular, to helical. This extensive range of shapes and their subsequent applications has piqued the curiosity of the scientific community, who now creatively compete to develop selective and direct routes to these valuable molecular architectures. Potential applications of these diverse domains have also driven the development of strategies for the installation of various substituents at selected sites of the carbon backbone. This review intends to provide the reader with an up-to-date overview of the methods for constructing extended fluorenones and their properties. Damien Prim studied chemistry at the Paul Verlaine University of Metz, where he received his Ph.D. in organic chemistry in 1994 under the guidance of Prof. Gilbert Kirsch. After a postdoctoral period with Prof. Léon Ghosez at UC Louvain-la-Neuve, Belgium, he was appointed as an assistant professor at Paul Verlaine University of Metz. In 1999, he moved to Pierre et Marie Curie University in Paris as a CNRS research associate. He then moved to the University of Versailles St Quentin as an assistant professor in 2001. In 2005, he was appointed as a full professor of chemistry at the University of Versailles St Quentin. Since 2020, he has been head of the Graduate School of Chemistry at the University of Paris-Saclay. His research focuses on homogeneous and heterogenous catalysis and the syntheses and properties of polycyclic molecular architectures. Benjamin Large studied chemistry at the Ecole Nationale Supérieure de Chimie de Montpellier, France, and then joined Damien Prim's team at the University of Versailles St Quentin as a Ph.D. student. His thesis was focused on the selective C-H functionalization of naphthalene and its derivatives. After obtaining his Ph.D. in 2019, Benjamin joined Anne-Kathrin Duhme-Klair's team as a postdoctoral research associate at the University of York (UK), and is currently working on the development of artificial metalloenzymes

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Fulvalene Derivatives Containing a Tetrabenzofluorene Unit: New Nonplanar Fulvalenes with High Electron Affinity

Cited by 4 publications

References 11 publications

Synthesis, structural analysis, and properties of highly twisted alkenes 13,13’-bis(dibenzo[a,i]fluorenylidene) and its derivatives

Synthesis, structural analysis, and properties of highly twisted alkenes 13,13’-bis(dibenzo[a,i]fluorenylidene) and its derivatives

Mechanochemical Scholl Reaction on Phenylated Cyclopentadiene Core: One‐Step Synthesis of Fluoreno[5]helicenes

On the Shape and Synthesis of Extended Fluorenones: Recent Advances and Upcoming Challenges

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