Electrocrystallization, an invaluable tool for the construction of ordered, electroactive molecular solids

For the past three decades, the electrocrystallization technique has been used extensively to assemble a large variety of molecular ions into long range ordered single crystals of high purity. This effort is reviewed in the present paper from the initial vigorous impetus triggered by the development of organic (molecular) metals and superconductors to the continuous diverse developments toward insulating antiferromagnetic systems, the synthesis of crystals of coordination polymers, the construction of ternary and quaternary phases, the variation of molecular conformation, the use of polyfunctionalized pi-donor molecules with hydrogen-bond-donor and/or -acceptor capabilities and the development of molecular alloys, with the aim of exemplifying an approach to the solid-state chemistry of molecular ions.