Tuning the optoelectronic properties of core-substituted naphthalene diimides by the selective conversion of imides to monothioimidesElectronic supplementary information (ESI) available: Experimental details, NMR spectra, MALDI-TOF MS spectra, XRD of RF2-1S, and computational data. CCDC 1056142. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5ra05920h

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 λ 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 NDI-based materials. Molecules with a low optical gap and high electron affinity were obtained via selective thionation of the distal carbonyls of 2,6-dialkylamino core-substituted naphthalene diimide.