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Title: Benzoimidazolium-derived dimeric and hydride n-dopants for organic electron-transport materials: impact of substitution on structures, electrochemistry, and reactivity

Journal Article · · Beilstein Journal of Organic Chemistry
DOI:https://doi.org/10.3762/bjoc.19.121· OSTI ID:2204445
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1,3-Dimethyl-2,3-dihydrobenzo[ d ]imidazoles, 1H , and 1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[ d ]imidazoles, 1 2 , are of interest as n-dopants for organic electron-transport materials. Salts of 2-(4-(dimethylamino)phenyl)-4,7-dimethoxy-, 2-cyclohexyl-4,7-dimethoxy-, and 2-(5-(dimethylamino)thiophen-2-yl)benzo[ d ]imidazolium ( 1g–i + , respectively) have been synthesized and reduced with NaBH 4 to 1gH , 1hH , and 1iH , and with Na:Hg to 1g 2 and 1h 2 . Their electrochemistry and reactivity were compared to those derived from 2-(4-(dimethylamino)phenyl)- ( 1b + ) and 2-cyclohexylbenzo[ d ]imidazolium ( 1e + ) salts. E ( 1 + / 1 • ) values for 2-aryl species are less reducing than for 2-alkyl analogues, i.e., the radicals are stabilized more by aryl groups than the cations, while 4,7-dimethoxy substitution leads to more reducing E ( 1 + / 1 • ) values, as well as cathodic shifts in E ( 1 2 •+ / 1 2 ) and E ( 1H •+ / 1H ) values. Both the use of 3,4-dimethoxy and 2-aryl substituents accelerates the reaction of the 1H species with PC 61 BM. Because 2-aryl groups stabilize radicals, 1b 2 and 1g 2 exhibit weaker bonds than 1e 2 and 1h 2 and thus react with 6,13-bis(triisopropylsilylethynyl)pentacene ( VII ) via a “cleavage-first” pathway, while 1e 2 and 1h 2 react only via “electron-transfer-first”. 1h 2 exhibits the most cathodic E ( 1 2 •+ / 1 2 ) value of the dimers considered here and, therefore, reacts more rapidly than any of the other dimers with VII via “electron-transfer-first”. Crystal structures show rather long central C–C bonds for 1b 2 (1.5899(11) and 1.6194(8) Å) and 1h 2 (1.6299(13) Å).

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF); United States-India Educational Foundation (USIEF)
Grant/Contract Number:
LDRD Program; AC36-08GO28308; DMR-1807797/2216857; DMR-2122108; 2266/FNPDR/2017
OSTI ID:
2204445
Alternate ID(s):
OSTI ID: 2204446; OSTI ID: 2222411
Report Number(s):
NREL/JA-5900-86656; BJOCBH
Journal Information:
Beilstein Journal of Organic Chemistry, Journal Name: Beilstein Journal of Organic Chemistry Vol. 19; ISSN 1860-5397
Publisher:
Beilstein InstitutCopyright Statement
Country of Publication:
Germany
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
benzoimidazole
crystal structure
kinetics
n-dopant
reduction