Stepwise reduction of an asymmetric π-expanded pyracylene towards the crystalline radical trianion

Zhu, Yikun; Borstelmann, Jan; Neiss, Christian; Wei, Zheng; Görling, Andreas; Kivala, Milan; Petrukhina, Marina A.

doi:10.1039/D4SC08255A

Title: Stepwise reduction of an asymmetric π-expanded pyracylene towards the crystalline radical trianion

Journal Article · 31 December 2024 · Chemical Science

DOI: https://doi.org/10.1039/D4SC08255A · OSTI ID:2504018

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Department of Chemistry, University at Albany, State University of New York, Albany, New York 12222, USA
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Lehrstuhl für Theoretische Chemie, Friedrich-Alexander Universität Erlangen-Nürnberg (FAU), Egerlandstraße 3, 91058 Erlangen, Germany
Lehrstuhl für Theoretische Chemie, Friedrich-Alexander Universität Erlangen-Nürnberg (FAU), Egerlandstraße 3, 91058 Erlangen, Germany, Erlangen National High Performance Computing Center (NHR@FAU), Martensstr. 1, 91058 Erlangen, Germany

The stepwise reduction by 1–3 electrons of a π-expanded pyracylene with K and Rb reveals that in-build core asymmetry affects the spin-density distribution in the mono- and trianion radicals, as confirmed by EPR spectroscopy and DFT calculations.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2504018

Journal Information:: Chemical Science, Journal Name: Chemical Science; ISSN 2041-6520; ISSN CSHCBM

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

References (46)

Clamshell Opening in the Mixed-Metal Supramolecular Aggregates Formed by Fourfold Reduced Corannulene for Maximizing Intercalated Metal Content Filatov, Alexander S.; Zabula, Alexander V.; Spisak, Sarah N. Angewandte Chemie International Edition, Vol. 53, Issue 1 https://doi.org/10.1002/anie.201308090	journal	November 2013
Electron‐Deficient Tetrabenzo‐Fused Pyracylene and Conversions into Curved and Planar π‐Systems Having Distinct Emission Behaviors Angewandte Chemie International Edition, Vol. 54, Issue 32 https://doi.org/10.1002/anie.201503783	journal	June 2015
Charging OBO-Fused Double [5]Helicene with Electrons Zhou, Zheng; Wang, Xiao-Ye; Wei, Zheng Angewandte Chemie International Edition, Vol. 58, Issue 42 https://doi.org/10.1002/anie.201908658	journal	September 2019
Reduction of π‐Expanded Cyclooctatetraene with Lithium: Stabilization of the Tetra‐Anion through Internal Li⁺ Coordination Zhou, Zheng; Zhu, Yikun; Wei, Zheng Angewandte Chemie International Edition, Vol. 60, Issue 7 https://doi.org/10.1002/anie.202013353	journal	December 2020
Stepwise Generation of Mono‐, Di‐, and Triply‐Reduced Warped Nanographenes: Charge‐Dependent Aromaticity, Surface Nonequivalence, Swing Distortion, and Metal Binding Sites Spisak, Sarah N.; Zhou, Zheng; Liu, Shuyang Angewandte Chemie International Edition, Vol. 60, Issue 48 https://doi.org/10.1002/anie.202110748	journal	October 2021
Site‐Specific Reduction‐Induced Hydrogenation of a Helical Bilayer Nanographene with K and Rb Metals: Electron Multiaddition and Selective Rb⁺ Complexation Zhou, Zheng; Fernández‐García, Jesús M.; Zhu, Yikun Angewandte Chemie International Edition, Vol. 61, Issue 10 https://doi.org/10.1002/anie.202115747	journal	December 2021
A Negatively Curved π‐Expanded Pyracylene Comprising a Tropylium Cation Borstelmann, Jan; Bergner, John; Rominger, Frank Angewandte Chemie International Edition, Vol. 62, Issue 46 https://doi.org/10.1002/anie.202312740	journal	October 2023
Fusing a Planar Group to a π-Bowl: Electronic and Molecular Structure, Aromaticity and Solid-State Packing of Naphthocorannulene and its Anions Zhou, Zheng; Spisak, Sarah N.; Xu, Qi Chemistry - A European Journal, Vol. 24, Issue 14 https://doi.org/10.1002/chem.201705814	journal	February 2018
Inducing Curvature to Pyracylene upon π‐Expansion Bergner, John; Walla, Christian; Rominger, Frank Chemistry – A European Journal, Vol. 28, Issue 47 https://doi.org/10.1002/chem.202201554	journal	July 2022
Ring currents and magnetic properties of pyracylene Fowler, P. W.; Zanasi, R.; Cadioli, B. Chemical Physics Letters, Vol. 251, Issue 3-4 https://doi.org/10.1016/0009-2614(96)00120-0	journal	March 1996
Planar, curved and twisted molecular nanographenes: Reduction-induced alkali metal coordination Zhou, Zheng; Petrukhina, Marina A. Coordination Chemistry Reviews, Vol. 486 https://doi.org/10.1016/j.ccr.2023.215144	journal	July 2023
Integrating pyracylene and naphthalenediimides into planar structures: Synthesis and characterization Cui, Xiaoping; Zhang, Guowei; Zhang, Lei Dyes and Pigments, Vol. 168 https://doi.org/10.1016/j.dyepig.2019.04.070	journal	September 2019
Synthesis and structural characterization of a trispyrrole iron(II) complex K(dme)4[tpaMesFe] and application in nitrous oxide dependent coupling reactions Weidauer, Maik; Irran, Elisabeth; Enthaler, Stephan Inorganic Chemistry Communications, Vol. 54 https://doi.org/10.1016/j.inoche.2015.01.028	journal	April 2015
Chemical reduction of indenocorannulene: A two-electron addition stop Zhu, Yikun; Zhou, Zheng; Wei, Zheng Journal of Organometallic Chemistry, Vol. 999 https://doi.org/10.1016/j.jorganchem.2023.122805	journal	October 2023
Record Alkali Metal Intercalation by Highly Charged Corannulene Zabula, Alexander V.; Spisak, Sarah N.; Filatov, Alexander S. Accounts of Chemical Research, Vol. 51, Issue 6 https://doi.org/10.1021/acs.accounts.8b00141	journal	May 2018
Triply-Reduced Hexa-peri-hexabenzocoronenes: Solid-State Structures and Magnetic Properties Zhou, Zheng; Wei, Zheng; Yao, Xuelin Crystal Growth & Design, Vol. 23, Issue 2 https://doi.org/10.1021/acs.cgd.2c01294	journal	January 2023
Fulleretic Materials: Buckyball- and Buckybowl-Based Crystalline Frameworks Rice, Allison M.; Dolgopolova, Ekaterina A.; Shustova, Natalia B. Chemistry of Materials, Vol. 29, Issue 17 https://doi.org/10.1021/acs.chemmater.7b02245	journal	August 2017
Structural Consequences of Two-Fold Deprotonation of Sumanene: Embedding Two Cp-rings into a Nonplanar Carbon Framework Zhou, Zheng; Wei, Zheng; Hirao, Toshikazu Organometallics, Vol. 40, Issue 13 https://doi.org/10.1021/acs.organomet.1c00295	journal	June 2021
Electronic structure, conductivity and superconductivity of alkali metal doped (C60) Haddon, R. C. Accounts of Chemical Research, Vol. 25, Issue 3 https://doi.org/10.1021/ar00015a005	journal	March 1992
Novel chemical species: radical trianions Gerson, Fabian; Huber, Walter Accounts of Chemical Research, Vol. 20, Issue 3 https://doi.org/10.1021/ar00135a002	journal	March 1987
Crystallographic studies of inter- and intramolecular interactions reflected in aromatic character of .pi.-electron systems Krygowski, Tadeusz Marek Journal of Chemical Information and Modeling, Vol. 33, Issue 1 https://doi.org/10.1021/ci00011a011	journal	January 1993
Electrochemical intercalation of lithium into solid fullerene C60 Chabre, Yves; Djurado, David; Armand, Michel Journal of the American Chemical Society, Vol. 114, Issue 2 https://doi.org/10.1021/ja00028a056	journal	January 1992
Electrochemical detection of C606- and C706-: Enhanced stability of fullerides in solution Xie, Qingshan; Perez-Cordero, Eduardo; Echegoyen, Luis Journal of the American Chemical Society, Vol. 114, Issue 10 https://doi.org/10.1021/ja00036a056	journal	May 1992
On the question of paramagnetic "ring currents" in pyracylene and related molecules Coulson, C. A.; Mallion, R. B. Journal of the American Chemical Society, Vol. 98, Issue 2 https://doi.org/10.1021/ja00418a045	journal	January 1976
Perturbed [12]annulenes. Synthesis of pyracylenes Trost, Barry M.; Bright, G. Michael; Frihart, Charles Journal of the American Chemical Society, Vol. 93, Issue 3 https://doi.org/10.1021/ja00732a031	journal	February 1971
Pyracylene. Pentalenoid system Trost, Barry M.; Bright, G. Michael. Journal of the American Chemical Society, Vol. 89, Issue 16 https://doi.org/10.1021/ja00992a064	journal	August 1967
The Aromaticity of Pyracylene: An Experimental and Computational Study of the Energetics of the Hydrogenation of Acenaphthylene and Pyracylene Diogo, Hermínio P.; Kiyobayashi, Tetsu; Minas da Piedade, Manuel E. Journal of the American Chemical Society, Vol. 124, Issue 9 https://doi.org/10.1021/ja012541+	journal	February 2002
Charging a Negatively Curved Nanographene and Its Covalent Network Zhang, Yiqun; Zhu, Yikun; Lan, Danni Journal of the American Chemical Society, Vol. 143, Issue 13 https://doi.org/10.1021/jacs.1c01642	journal	March 2021
Unveiling the Multielectron Acceptor Properties of π-Expanded Pyracylene: Reversible Boat to Chair Conversion Zhu, Yikun; Borstelmann, Jan; Bertleff, Oliver Journal of the American Chemical Society, Vol. 146, Issue 21 https://doi.org/10.1021/jacs.4c02314	journal	May 2024
A New Suzuki−Heck-Type Coupling Cascade: Indeno[1,2,3]-Annelation of Polycyclic Aromatic Hydrocarbons Wegner, Hermann A.; Scott, Lawrence T.; de Meijere, Armin The Journal of Organic Chemistry, Vol. 68, Issue 3 https://doi.org/10.1021/jo020367h	journal	January 2003
Local Aromaticity of the Six-Membered Rings in Pyracylene. A Difficult Case for the NICS Indicator of Aromaticity Poater, Jordi; Solà, Miquel; Viglione, Rosario G. The Journal of Organic Chemistry, Vol. 69, Issue 22 https://doi.org/10.1021/jo048988t	journal	October 2004
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model Barone, Vincenzo; Cossi, Maurizio The Journal of Physical Chemistry A, Vol. 102, Issue 11 https://doi.org/10.1021/jp9716997	journal	March 1998
bis-peri-Phenylenenaphthalene Clar, E.; Stubbs, H. W. D.; Tucker, S. Horwood Nature, Vol. 166, Issue 4234 https://doi.org/10.1038/1661075c0	journal	December 1950
Bulk superconductivity at 38 K in a molecular system Ganin, Alexey Y.; Takabayashi, Yasuhiro; Khimyak, Yaroslav Z. Nature Materials, Vol. 7, Issue 5, p. 367-371 https://doi.org/10.1038/nmat2179	journal	April 2008
Ge ₅ ²⁻ Zintl anions: synthesis and crystal structures of [K([2.2.2]-crypt)] ₂ Ge ₅ ·4NH ₃ and [Rb([2.2.2]-crypt)] ₂ Ge ₅ ·4NH ₃ Suchentrunk, Christof; Korber, Nikolaus New J. Chem., Vol. 30, Issue 12 https://doi.org/10.1039/B610547E	journal	January 2006
Tuning the separation and coupling of corannulene trianion-radicals through sizable alkali metal belts Spisak, Sarah N.; Rogachev, Andrey Yu.; Zabula, Alexander V. Chemical Science, Vol. 8, Issue 4 https://doi.org/10.1039/C6SC05370J	journal	January 2017
Stepwise deprotonation of sumanene: electronic structures, energetics and aromaticity alterations Xu, Qi; Petrukhina, Marina A.; Rogachev, Andrey Yu. Physical Chemistry Chemical Physics, Vol. 19, Issue 32 https://doi.org/10.1039/C7CP03549G	journal	January 2017
Acenaphthylene as a building block for π-electron functional materials Liu, Ying-Hsuan; Perepichka, Dmitrii F. Journal of Materials Chemistry C, Vol. 9, Issue 37 https://doi.org/10.1039/D1TC02826J	journal	January 2021
Reversible structural rearrangement of π-expanded cyclooctatetraene upon two-fold reduction with alkali metals Zhou, Zheng; Zhu, Yikun; Wei, Zheng Chemical Communications, Vol. 58, Issue 19 https://doi.org/10.1039/D2CC00218C	journal	January 2022
Crystallographic evidence for global aromaticity in the di-anion and tetra-anion of a cyclophane hydrocarbon Stawski, Wojciech; Zhu, Yikun; Wei, Zheng Chemical Science, Vol. 14, Issue 48 https://doi.org/10.1039/D3SC04251K	journal	January 2023
Stepwise deprotonation of truxene: structures, metal complexation, and charge-dependent optical properties Guo, Yumeng; Torchon, Herdya S.; Zhu, Yikun Chemical Science, Vol. 14, Issue 45 https://doi.org/10.1039/D3SC04885C	journal	January 2023
Reduced corannulenes: 1,8-dicorannulenyloctane anions, a supramolecular octaanion Shabtai, Elad; Hoffman, Roy E.; Cheng, Pei-Chao Journal of the Chemical Society, Perkin Transactions 2, Issue 1 https://doi.org/10.1039/a905403k	journal	January 2000
651. Synthesis of fluoranthenes. Part VII. 1 : 2-5 : 6-Dibenzopyracylene Stubbs, H. W. D.; Tucker, S. Horwood Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9510002936	journal	January 1951
The Disorder-Free Non-BCS Superconductor Cs3C60 Emerges from an Antiferromagnetic Insulator Parent State Takabayashi, Y.; Ganin, A. Y.; Jeglic, P. Science, Vol. 323, Issue 5921 https://doi.org/10.1126/science.1169163	journal	March 2009
Synthesis and crystal structures of (2.2.2-cryptand)rubidium chloride and bromide hydrates Chekhlov, A. N. Russian Journal of Coordination Chemistry, Vol. 33, Issue 7 https://doi.org/10.1134/S1070328407070020	journal	July 2007
Wechselwirkungen in Molekülkristallen, 163 [1, 2]. Einfluß der Alkalimetall-Reduktionspotentiale auf die Bildung ihrer Kontaktionenmultipel mit Tetracen- und Decacylen-Polyanionen / Interaction in Molecular Crystals, 163 [ 1,2]. The Influence of Alkaline Metal Reduction Potentials on the Formation of their Contaction Multiples with Tetracene and Decacyclene Polyanions Bock, Hans; Gharagozloo-Hubmann, K.; Holl, S. Zeitschrift für Naturforschung B, Vol. 55, Issue 12 https://doi.org/10.1515/znb-2000-1210	journal	December 2000

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