Organometallic hydride-transfer agents as reductants for organic semiconductor molecules

• Published in: Inorganica Chimica Acta 2019-04, Vol.489, p.67-77
• Main Authors: Zhang, Siyuan, Moudgil, Karttikay, Jucov, Evgheni, Risko, Chad, Timofeeva, Tatiana V., Marder, Seth R., Barlow, Stephen
• Format: Article
• Language: English
• Subjects: Aromatic compounds; Borates; Coordination compounds; Crystal structure; Density functional theory; Derivatives; Diimide; Dimers; Electrochemistry; Fullerenes; Hydride donor; Hydrides; Iridium; Metallocene; Organic semiconductors; Rhodium; Ruthenium; Semiconductors
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2019.02.003

[Display omitted] •Two classes of organometallic hydride donors are compared.•Hydride donors are compared to corresponding dimeric electron donors.•RuCp*(mesH) is a particularly strong hydride donor.•Crystal structures are reported for metallocenyl organic hydride donors. Both organic hydride donors, DH, and the dimers formed by some organic radicals and by some 19-electron organometallic sandwich compounds, D2, have recently been examined extensively as n-dopants for organic semiconductors. This properties of two classes of organometallic DH derivatives – organic DH derivatives with metallocenyl substituents and species obtained by hydride reduction of 18-electron D+ sandwich cations – are discussed and compared to those of the corresponding D2 molecules. 1,3-Dimethyl-2-metallocenyl-2,3-dihydro-1H-benzo[d]imidazoles, Mc-DMBI-H (Mc = ferrocenyl [Fc], ruthenocenyl [Rc]), and 1,3-dimethyl-2-phenyl-1H-benzo[d]imidazolium tetrakis(3,5-bis(trifluoromethyl))borates, Mc-DMBI+BAr'4– (Mc = Fc, Rc), have recently been reported as intermediates in the synthesis of the dimers (Mc-DMBI)2; here their crystal structures are reported and compared to those of related molecules. The solution reactivity of the Mc-DMBI-H derivatives with a fullerene acceptor is similar to that of purely organic aryl-DMBI-H species. Previously reported (exo-H-η4-pentamethylcyclopentadiene)(η5-cyclopentadienyl)metal complexes, M(exo-H-Cp*H)Cp (M = Rh, Ir) and the new (η5-pentamethylcyclopentadienyl)(η5-1,3,5-trimethylcyclohexa-1,3-dien-5-yl)ruthenium, RuCp*(mesH), have also been examined as potential reductants for organic semiconductors; RuCp*(mesH) is particularly reactive, affording the radical anions of perylene diimide and 6,13-bis(tri(isopropyl)silylethynyl)pentacene. The electrochemistry of DH, D+, and D2 species is compared for the five compounds. Density-functional theory calculations are used to gain insight into the trends in electrochemistry and reactivity.