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The ionic character of a set of two redox linkages and strong, directional halogen bonding at the organic–inorganic interface compromise to produce two materials sharing a common two-dimensional net, eventually extended in a third dimension, although two of the six symmetrical halogen bond acceptors ultimately remain uninvolved as a result of charge densification.

The redox active ligand EDT-TTF-CONH-3-pyridine undergoes a 2 2 cycloaddition upon irradiation with polychromatic light, an unprecedented single-crystal-to-single-crystal transformation for a TTF derivative.

Neutral π-conjugated molecules and their radical cations co-exist in EDT-TTF-CONHMe4EDT-TTF-CONHMe02 Re6Se8CN64−CH3CN2CH2Cl22whose 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.

Neutral π-conjugated molecules and their radical cations co-exist in [(EDT-TTF-CONHMe+&z.rad;)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.

Comparison within the title [Re₆Q₈X₆]4−/[Re₆Q₈X₆]3− redox series of 14 precise crystal structures of the Re₆ cluster cores at different low temperatures reveals that the one-electron oxidised, open-shell (23 electron) cores undergo a Jahn–Teller distortion of their parent 24 electron octahedral cores and that D_4h and D_2h forms may co-exist in the solid state.