Beyond n-dopants for organic semiconductors: use of bibenzo[ d ]imidazoles in UV-promoted dehalogenation reactions of organic halides

Tang, Kan; Brown, Megan R.; Risko, Chad; Gish, Melissa K.; Rumbles, Garry; Pham, Phuc H.; Luca, Oana R.; Barlow, Stephen; Marder, Seth R.

doi:10.3762/bjoc.19.142

Title: Beyond n-dopants for organic semiconductors: use of bibenzo[ d ]imidazoles in UV-promoted dehalogenation reactions of organic halides

Journal Article · 13 December 2023 · Beilstein Journal of Organic Chemistry

DOI: https://doi.org/10.3762/bjoc.19.142 · OSTI ID:2229962

;

; Gish, Melissa K.; Rumbles, Garry;

;

2,2’-Bis(4-dimethylaminophenyl)- and 2,2'-dicyclohexyl-1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[ d ]imidazole ((N-DMBI) ₂ and (Cyc-DMBI) ₂ ) are quite strong reductants with effective potentials of ca. −2 V vs ferrocenium/ferrocene, yet are relatively stable to air due to the coupling of redox and bond-breaking processes. Here, we examine their use in accomplishing electron transfer-induced bond-cleavage reactions, specifically dehalogenations. The dimers reduce halides that have reduction potentials less cathodic than ca. −2 V vs ferrocenium/ferrocene, especially under UV photoexcitation (using a 365 nm LED). In the case of benzyl halides, the products are bibenzyl derivatives, whereas aryl halides are reduced to the corresponding arenes. The potentials of the halides that can be reduced in this way, quantum-chemical calculations, and steady-state and transient absorption spectroscopy suggest that UV irradiation accelerates the reactions via cleavage of the dimers to the corresponding radical monomers.

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Sponsoring Organization:: USDOE

OSTI ID:: 2229962

Alternate ID(s):: OSTI ID: 2229965; OSTI ID: 2274753; OSTI ID: 2282708

Journal Information:: Beilstein Journal of Organic Chemistry, Journal Name: Beilstein Journal of Organic Chemistry Vol. 19; ISSN 1860-5397; ISSN BJOCBH

Publisher:: Beilstein InstitutCopyright Statement

Country of Publication:: Germany

Language:: English

References (44)

Identifying the Roles of Amino Acids, Alcohols and 1,2-Diamines as Mediators in Coupling of Haloarenes to Arenes Zhou, Shengze; Doni, Eswararao; Anderson, Greg M. Journal of the American Chemical Society, Vol. 136, Issue 51 https://doi.org/10.1021/ja5101036	journal	December 2014
Highly reactive magnesium and its application to organic syntheses Burns, Timothy P.; Rieke, Reuben D. The Journal of Organic Chemistry, Vol. 52, Issue 16 https://doi.org/10.1021/jo00392a033	journal	August 1987
Formation kinetics of an amino carboxy type merostabilized free radical Bennett, Richard W.; Wharry, Donald L.; Koch, Tad H. Journal of the American Chemical Society, Vol. 102, Issue 7 https://doi.org/10.1021/ja00527a036	journal	March 1980
Efficient Solution-Processed n-Type Small-Molecule Thermoelectric Materials Achieved by Precisely Regulating Energy Level of Organic Dopants Yuan, Dafei; Huang, Dazhen; Zhang, Cheng ACS Applied Materials & Interfaces, Vol. 9, Issue 34 https://doi.org/10.1021/acsami.7b07282	journal	August 2017
Understanding the Effects of Molecular Dopant on n‐Type Organic Thermoelectric Properties Un, Hio‐Ieng; Gregory, Shawn A.; Mohapatra, Swagat K. Advanced Energy Materials, Vol. 9, Issue 24 https://doi.org/10.1002/aenm.201900817	journal	May 2019
Pushing the Limits of Neutral Organic Electron Donors: A Tetra(iminophosphorano)-Substituted Bispyridinylidene Hanson, Samuel S.; Doni, Eswararao; Traboulsee, Kyle T. Angewandte Chemie International Edition, Vol. 54, Issue 38 https://doi.org/10.1002/anie.201505378	journal	July 2015
Organometallic and Organic Dimers: Moderately Air-Stable, Yet Highly Reducing, n-Dopants Mohapatra, Swagat K.; Marder, Seth R.; Barlow, Stephen Accounts of Chemical Research, Vol. 55, Issue 3 https://doi.org/10.1021/acs.accounts.1c00612	journal	January 2022
Effective Solution- and Vacuum-Processed n-Doping by Dimers of Benzimidazoline Radicals Naab, Benjamin D.; Zhang, Siyuan; Vandewal, Koen Advanced Materials, Vol. 26, Issue 25 https://doi.org/10.1002/adma.201400668	journal	April 2014
Kinetics and mechanism of oxidation of N,N′-dimethyl-9,9′-biacridanyl by some π acceptors and a one-electron oxidant Colter, Allan K.; Lai, Charles C.; Parsons, A. Gregg Canadian Journal of Chemistry, Vol. 63, Issue 2 https://doi.org/10.1139/v85-073	journal	February 1985
Luminescent tungsten(vi) complexes as photocatalysts for light-driven C–C and C–B bond formation reactions Yu, Daohong; To, Wai-Pong; Tong, Glenna So Ming Chemical Science, Vol. 11, Issue 25 https://doi.org/10.1039/d0sc01340d	journal	January 2020
n-Dopants Based on Dimers of Benzimidazoline Radicals: Structures and Mechanism of Redox Reactions Zhang, Siyuan; Naab, Benjamin D.; Jucov, Evgheni V. Chemistry - A European Journal, Vol. 21, Issue 30 https://doi.org/10.1002/chem.201500611	journal	June 2015
Molecular parameters responsible for thermally activated transport in doped organic semiconductors Schwarze, Martin; Gaul, Christopher; Scholz, Reinhard Nature Materials, Vol. 18, Issue 3 https://doi.org/10.1038/s41563-018-0277-0	journal	January 2019
Generation of powerful organic electron donors by water-assisted decarboxylation of benzimidazolium carboxylates Tintori, Guillaume; Fall, Arona; Assani, Nadhrata Organic Chemistry Frontiers, Vol. 8, Issue 6 https://doi.org/10.1039/d0qo01488e	journal	January 2021
Reduction of aryl halides by consecutive visible light-induced electron transfer processes Ghosh, I.; Ghosh, T.; Bardagi, J. I. Science, Vol. 346, Issue 6210 https://doi.org/10.1126/science.1258232	journal	November 2014
A simple approach to C3-ethoxycarbonylmethylation of thiophenes/furans with diethyl bromomalonate Huang, Mengmeng; Tang, Jingzhou; Kim, Jung Keun Organic & Biomolecular Chemistry, Vol. 20, Issue 32 https://doi.org/10.1039/d2ob00835a	journal	January 2022
Spectral Signatures of a Negative Polaron in a Doped Polymer Semiconductor: Energy Levels and Hubbard U Interactions Lungwitz, Dominique; Joy, Syed; Mansour, Ahmed E. The Journal of Physical Chemistry Letters, Vol. 14, Issue 24 https://doi.org/10.1021/acs.jpclett.3c01022	journal	June 2023
Electron transport in a sequentially doped naphthalene diimide polymer Al Kurdi, Khaled; Gregory, Shawn A.; Jhulki, Samik Materials Advances, Vol. 1, Issue 6 https://doi.org/10.1039/d0ma00406e	journal	January 2020
Direct preparation of benzylic manganese reagents from benzyl halides, sulfonates, and phosphates and their reactions: applications in organic synthesis Suh, YoungSung; Lee, Jun-sik; Kim, Seoung-Hoi Journal of Organometallic Chemistry, Vol. 684, Issue 1-2 https://doi.org/10.1016/s0022-328x(03)00500-x	journal	November 2003
Highly reactive metallic nickel: reductive homocoupling reagent for benzylic mono- and polyhalides Inaba, Shinichi; Matsumoto, Hideyuki; Rieke, Reuben D. The Journal of Organic Chemistry, Vol. 49, Issue 12 https://doi.org/10.1021/jo00186a003	journal	June 1984
Organic super-electron-donors: initiators in transition metal-free haloarene–arene coupling Zhou, Shengze; Anderson, Greg M.; Mondal, Bhaskar Chem. Sci., Vol. 5, Issue 2 https://doi.org/10.1039/c3sc52315b	journal	January 2014
Reactivity of an air-stable dihydrobenzoimidazole n-dopant with organic semiconductor molecules Jhulki, Samik; Un, Hio-Ieng; Ding, Yi-Fan Chem, Vol. 7, Issue 4 https://doi.org/10.1016/j.chempr.2021.01.020	journal	April 2021
Super-Electron Donors: Bis-pyridinylidene Formation by Base Treatment of Pyridinium Salts Murphy, John A.; Garnier, Jean; Park, Stuart R. Organic Letters, Vol. 10, Issue 6 https://doi.org/10.1021/ol800134g	journal	March 2008
Role of Polymer Structure on the Conductivity of N-Doped Polymers Naab, Benjamin D.; Gu, Xiaodan; Kurosawa, Tadanori Advanced Electronic Materials, Vol. 2, Issue 5 https://doi.org/10.1002/aelm.201600004	journal	March 2016
Correlation of Hydrogen-Atom Abstraction Reaction Efficiencies for Aryl Radicals with their Vertical Electron Affinities and the Vertical Ionization Energies of the Hydrogen-Atom Donors Jing, Linhong; Nash, John J.; Kenttämaa, Hilkka I. Journal of the American Chemical Society, Vol. 130, Issue 52 https://doi.org/10.1021/ja801707p	journal	December 2008
Aminoalkyl radicals as halogen-atom transfer agents for activation of alkyl and aryl halides Constantin, Timothée; Zanini, Margherita; Regni, Alessio Science, Vol. 367, Issue 6481 https://doi.org/10.1126/science.aba2419	journal	February 2020
Electricity-driven recycling of ester plastics using one-electron electro-organocatalysis Pham, Phuc H.; Barlow, Stephen; Marder, Seth R. Chem Catalysis, Vol. 3, Issue 8 https://doi.org/10.1016/j.checat.2023.100675	journal	August 2023
Untersuchungen zur reaktivität organometallischer komplexe III. Über die reaktion von dicyclopentadienylkobalt mit halogenmethanen Herberich, G. E.; Bauer, E.; Schwarzer, J. Journal of Organometallic Chemistry, Vol. 17, Issue 3 https://doi.org/10.1016/s0022-328x(00)88230-3	journal	June 1969
Photochemical Reductive C–C Coupling with a Guanidine Electron Donor Wiesner, Sven; Walter, Petra; Wagner, Arne European Journal of Organic Chemistry, Vol. 2016, Issue 29 https://doi.org/10.1002/ejoc.201600978	journal	September 2016
Electrogenerated chemiluminescence in mechanistic investigations of electroorganic reactions Pragst, F.; Niazymbetov, M. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 197, Issue 1-2 https://doi.org/10.1016/0022-0728(86)80153-x	journal	January 1986
Synthesis, structures, and reactivity of isomers of [RuCp*(1,4-(Me₂N)₂C₆H₄)]₂ Longhi, Elena; Risko, Chad; Bacsa, John Dalton Transactions, Vol. 50, Issue 37 https://doi.org/10.1039/d1dt02155a	journal	January 2021
Electron spin dynamics in excited state photochemistry: recent development in the study of intersystem crossing and charge transfer in organic compounds Imran, Muhammad; Zhang, Xue; Wang, Zhijia Physical Chemistry Chemical Physics, Vol. 23, Issue 30 https://doi.org/10.1039/d1cp01937f	journal	January 2021
Benzylic Manganese Halides, Sulfonates, and Phosphates: Preparation, Coupling Reactions, and Applications in Organic Synthesis Kim, Seung-Hoi; Rieke, Reuben D. The Journal of Organic Chemistry, Vol. 65, Issue 8 https://doi.org/10.1021/jo991478s	journal	March 2000
Understanding Kinetic Solvent Effects on Hydrogen Abstraction Reactions from Carbon by the Cumyloxyl Radical Bietti, Massimo; Martella, Roberto; Salamone, Michela Organic Letters, Vol. 13, Issue 22 https://doi.org/10.1021/ol202561z	journal	October 2011
Highly Efficient Reduction of Unactivated Aryl and Alkyl Iodides by a Ground-State Neutral Organic Electron Donor Murphy, John A.; Khan, Tanweer A.; Zhou, Sheng-ze Angewandte Chemie International Edition, Vol. 44, Issue 9 https://doi.org/10.1002/anie.200462038	journal	February 2005
Investigation of two radical intermediates in the anodic oxidation of 1,4-dihydropyridines by electrochemiluminescence Ludvík, Jir̆í; Volke, Jir̆í; Pragst, Fritz Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 215, Issue 1-2 https://doi.org/10.1016/0022-0728(86)87014-0	journal	December 1986
Electron-Transfer Photoredox Catalysis: Development of a Tin-Free Reductive Dehalogenation Reaction Narayanam, Jagan M. R.; Tucker, Joseph W.; Stephenson, Corey R. J. Journal of the American Chemical Society, Vol. 131, Issue 25 https://doi.org/10.1021/ja9033582	journal	July 2009
Benzoimidazolium-derived dimeric and hydride n-dopants for organic electron-transport materials: impact of substitution on structures, electrochemistry, and reactivity Mohapatra, Swagat K.; Al Kurdi, Khaled; Jhulki, Samik Beilstein Journal of Organic Chemistry, Vol. 19 https://doi.org/10.3762/bjoc.19.121	journal	November 2023
The Generation of Aryl Anions by Double Electron Transfer to Aryl Iodides from a Neutral Ground‐State Organic Super‐Electron Donor Murphy, John A.; Zhou, Sheng‐ze; Thomson, Douglas W. Angewandte Chemie International Edition, Vol. 46, Issue 27 https://doi.org/10.1002/anie.200700554	journal	June 2007
N-Hydroxypyridine-2-thione esters as radical precursors in kinetic studies. Measurements of rate constants for hydrogen-atom-abstraction reactions Newcomb, Martin.; Park, Seung Un. Journal of the American Chemical Society, Vol. 108, Issue 14 https://doi.org/10.1021/ja00274a046	journal	July 1986
Electrochemical generation of triplet states Ludvik, J.; Pragst, F.; Volke, J. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 180, Issue 1-2 https://doi.org/10.1016/0368-1874(84)83576-5	journal	December 1984
Nickel-Catalyzed Photodehalogenation of Aryl Bromides Martin, Ruben; Higginson, Bradley; Sanjosé-Orduna, Jesus Synlett, Vol. 32, Issue 16 https://doi.org/10.1055/a-1457-2399	journal	April 2021
n-Doping of Organic Electronic Materials Using Air-Stable Organometallics: A Mechanistic Study of Reduction by Dimeric Sandwich Compounds Guo, Song; Mohapatra, Swagat K.; Romanov, Alexander Chemistry - A European Journal, Vol. 18, Issue 46 https://doi.org/10.1002/chem.201202591	journal	October 2012
Bond Dissociation Energies of Organic Molecules Blanksby, Stephen J.; Ellison, G. Barney Accounts of Chemical Research, Vol. 36, Issue 4 https://doi.org/10.1021/ar020230d	journal	April 2003
Visible Light-Mediated Intermolecular C−H Functionalization of Electron-Rich Heterocycles with Malonates Furst, Laura; Matsuura, Bryan S.; Narayanam, Jagan M. R. Organic Letters, Vol. 12, Issue 13 https://doi.org/10.1021/ol101146f	journal	July 2010

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