Interdependence of redox state, hydrogen bonding, anion recognition and charge partition in crystals of (EDT-TTF-CONHMe) 6 [Re 6 Se 8 (CN) 6 ] (CH 3 CN) 2 (CH 2 Cl 2 ) 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.