Interdependence of redox state, hydrogen bonding, anion recognition and charge partition in crystals of (EDT-TTFCONHMe)6[Re6Se8(CN)6](CH3CN)2(CH2Cl2)2

Neutral (pi)-conjugated molecules and their radical cations co-exist in [(EDT-TTF-CONHMe+.)4(EDT-TTF-CONHMe0)2] [Re6Se8(CN)6]4–(CH3CN)2(CH2Cl2)2 whose crystal structure reveals that, upon one-electron oxidation, an activation of the N–H and C–H hydrogen bond donor ability is coupled to a deactivation of the hydrogen bond acceptor character of the carbonyl oxygen atom: this is expressed in the supramolecular hydrogen bond pattern and, ultimately, into charge localisation and partition in the solid state.