Tuning the optoelectronic properties of core-substituted naphthalene diimides by the selective conversion of imides to monothioimides

Abstract

Selective sulfur substitution of the distal carbonyls of a core-substituted naphthalene diimide was obtained when a combination of core and imide substituents were used. The substituents appear to inhibit thionation of the proximal carbonyl by steric hindrance. Each thionation caused a 50 nm bathochromic shift of the visible absorption band and an anodic shift of the reduction potentials. The dithionated compound has a l max in the near-IR at 733 nm and an optical gap of 1.59 eV, which is unusually low for this type of molecule. Thionation of carbonyls offers a useful avenue for tuning optoelectronic properties of NDIbased materials.

Thionated naphthalene diimides: tuneable chromophores for applications in photoactive dyads

“…23,24 Carbonyl groups of NDIs/NIs play a significant role in influencing the nature of the frontier orbitals of these species, therefore substitution with sulfur is likely to strongly affect the properties of these species. [25][26][27][28][29][30] Studies by Seferos et al, amongst others, report that the reaction of NDIs [25][26][27] , and their analogues PDIs 25,[28][29][30] , with Lawesson's reagent resulted in the substitution of the carbonyl oxygen atoms with sulfur atoms to give thionated dyes.…”

Enhanced electron mobility in crystalline thionated naphthalene diimides

“…electron transporting). [27][28][29][30][31][32] This so-called thionation typically results in a lowering of the LUMO energy and increase in electron affinity, satisfying the first design criterion for an ideal n-type OTFT material. 16,17 Many of the best-performing n-type materials for both OPVs and OTFTs contain an electron withdrawing carbonyl group in the form of an amide or imide functionality, 4,18-20 such as diketopyrrolopyrrole (DPP), 21,22 thieno [3,4-c]pyrrole-4,6-dione (TPD), 23 perylene diimide (PDI), 24 and naphthalene diimide (NDI).…”

Fluorination and chlorination effects on quinoxalineimides as an electron-deficient building block for n-channel organic semiconductors

“…The direct imidization of cyclic acid anhydride with alkylamine in heating N,N-dimethylformamide or acetic acid is commonly employed to prepare imide part such as naphthalenediimide (NDI). 39,40 However, in the case of QI, the direct imidization failed; this was likely because of the instability of 7a-d under harsh acidic or basic conditions at high temperatures. Alternatively, the mild reaction condition at room temperature using sequential amidation with the corresponding alkylamine following acid-chloridemediated cyclization with oxalyl chloride was found to form the target QI-based molecules 1-4 as a pale-yellow solid in relatively high yields (>73%).…”