Cations and Anions of Dibenzo[a,e]pentalene and Reduction of a Dibenzo[a,e]pentalenophane.
antiaromaticity
organic field-effect transistors
oxidation
radical anion
reduction
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
12 Mar 2021
12 Mar 2021
Historique:
received:
27
11
2020
pubmed:
15
1
2021
medline:
15
1
2021
entrez:
14
1
2021
Statut:
ppublish
Résumé
Dibenzo[a,e]pentalene (DBP) is a non-alternant conjugated hydrocarbon with antiaromatic character and ambipolar electrochemical behavior. Upon both reduction and oxidation, it becomes aromatic. We herein study the chemical oxidation and reduction of a planar DBP derivative and a bent DBP-phane. The molecular structures of its planar dication, cation radical and anion radical in the solid state demonstrate the gained aromaticity through bond length equalization, which is supported by nucleus independent chemical shift-calculations. EPR spectra on the cation radical confirm the spin delocalization over the DBP framework. A similar delocalization was not possible in the reduced bent DBP-phane, which stabilized itself by proton abstraction from a solvent molecule upon reduction. This is the first report on structures of a DBP cation radical and dication in the solid state and of a reduced bent DBP derivative. Our study provides valuable insight into the charged species of DBP for its application as semiconductor.
Identifiants
pubmed: 33443300
doi: 10.1002/chem.202005131
pmc: PMC7986162
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
4964-4970Subventions
Organisme : Deutsche Forschungsgemeinschaft
ID : 230408635
Organisme : Deutsche Forschungsgemeinschaft
ID : 434040413
Organisme : Deutsche Forschungsgemeinschaft
ID : 417643975
Organisme : Deutsche Forschungsgemeinschaft
ID : 2100302201
Organisme : Deutsche Forschungsgemeinschaft
ID : 431116391
Organisme : Deutsche Forschungsgemeinschaft
ID : INST 40/467-1 FUGG
Organisme : Deutsche Forschungsgemeinschaft
ID : INST 39/1081-1 FUGG
Informations de copyright
© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
Références
Angew Chem Int Ed Engl. 2011 Feb 1;50(5):1127-30
pubmed: 21268210
J Org Chem. 2020 Jan 3;85(1):34-43
pubmed: 31187987
Angew Chem Int Ed Engl. 2007;46(9):1504-7
pubmed: 17387657
Angew Chem Int Ed Engl. 2021 Jul 12;60(29):15743-15766
pubmed: 32902109
Chem Soc Rev. 2016 Feb 21;45(4):789-899
pubmed: 26612538
Chem Commun (Camb). 2015 Jan 11;51(3):503-6
pubmed: 25406768
Nat Chem. 2020 Jul;12(7):647-653
pubmed: 32572165
Chem Asian J. 2012 Mar 5;7(3):480-3
pubmed: 22247079
Angew Chem Int Ed Engl. 2020 Jun 8;59(24):9453-9459
pubmed: 32187797
Chempluschem. 2017 Jul;82(7):1039-1042
pubmed: 31961600
Phys Chem Chem Phys. 2015 Mar 21;17(11):7366-72
pubmed: 25700011
Angew Chem Int Ed Engl. 2010 Oct 11;49(42):7728-32
pubmed: 20836110
Angew Chem Int Ed Engl. 2017 Mar 13;56(12):3270-3274
pubmed: 28067436
Chemistry. 2019 Jan 2;25(1):216-220
pubmed: 30423210
J Am Chem Soc. 2015 Jun 10;137(22):7178-88
pubmed: 25978774
Chemistry. 2018 May 23;24(29):7374-7387
pubmed: 29528165
Angew Chem Int Ed Engl. 2013 Nov 18;52(47):12224-6
pubmed: 24127399
Dalton Trans. 2020 Jun 21;49(23):7766-7773
pubmed: 32329763
J Am Chem Soc. 2014 Jun 25;136(25):9181-9
pubmed: 24917380
J Org Chem. 2018 Jan 19;83(2):656-663
pubmed: 29231725
J Am Chem Soc. 1996 Jul 3;118(26):6317-6318
pubmed: 28872872
J Org Chem. 2016 Sep 16;81(18):8312-8
pubmed: 27559925
Chemistry. 2021 Mar 12;27(15):4964-4970
pubmed: 33443300
J Am Chem Soc. 2016 Dec 28;138(51):16827-16838
pubmed: 27966911
J Magn Reson. 2006 Jan;178(1):42-55
pubmed: 16188474
Chem Commun (Camb). 2015 Jan 14;51(4):693-6
pubmed: 25418778
Angew Chem Int Ed Engl. 2018 Oct 22;57(43):13982-14024
pubmed: 29266644
Angew Chem Int Ed Engl. 2013 Oct 4;52(41):10822-5
pubmed: 24810035
Angew Chem Int Ed Engl. 2021 May 3;60(19):10680-10689
pubmed: 33596338
Chem Sci. 2019 Jan 10;10(9):2821-2829
pubmed: 30997003
Chemistry. 2014 Jun 16;20(25):7571-5
pubmed: 24805124
Chemistry. 2015 Nov 16;21(47):17016-22
pubmed: 26420200
J Org Chem. 2016 Sep 2;81(17):7700-10
pubmed: 27467138
Chem Commun (Camb). 2021 Jan 26;57(6):745-748
pubmed: 33346282
Angew Chem Int Ed Engl. 2017 Nov 27;56(48):15363-15367
pubmed: 28985444