Synthesis of redox-active donor/acceptor chromophores with a central indenofluorene or indacenodithiophene core

[Display omitted] •Donor-acceptor systems with indenofluorene cores are made in stepwise olefinations.•A dithiafulvene/dicyanoethylene scaffold has a particularly low HOMO-LUMO gap.•An extended tetracyanoquinodimethane acceptor exhibits two reversible reductions.•An extended tetrathiafulvalene with an indacenodithiophene core is presented. Tetrathiafulvalene (TTF) and tetracyanoquinodimethane (TCNQ) are classical redox-active molecules that can be oxidized and reduced, respectively, in two one-electron steps. Herein we present the synthesis of a selection of extended derivatives based on either an indenofluorene or indacenodithiophene core and containing either two dithiafulvene units (extended TTF), two dicyanomethylene units (extended TCNQ) or one of each of these units (donor–acceptor system). The optical and redox properties of the molecules are also presented.