Electrocrystallization, an Invaluable Tool for the Construction of Ordered, Electroactive Molecular Solids

Abstract

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 π-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.

Structural Isomerism in Crystals of Redox‐Active Secondary ortho‐Diamides: The Role of Competing Intra‐ and Intermolecular Hydrogen Bonds in Directing Crystalline Topologies

“…Recent work along such lines has focused on the competition between interand intramolecular hydrogen bonding in the gas [20] and solution [21] phases. To probe the flexibility and fluxionality of TTF amide derivatives on lengthening the alkyl side chains, we report here on the synthesis and electrochemical and structural characterization of seven EDT-TTF-(CONHR) 2 (R = Me, 1; Et, 2; Pr, 3; Bu, 4; Pent, 5; Hex, 6, Bz, 7) and demonstrate that on electrocrystallization [22] with two similar tetrahedral anions, namely ReO 4 À and ClO 4 À , the methyl derivative 1 yields two salts of identical stoichiometry with very different crystal structures. Hence, by contrast with the stubborn proclivity of the primary diamide EDT-TTF-(CONH 2 ) 2 to direct the assemblage of only one ribbon of self-complementary intra-and intermolecular amide···amide ring motifs, yet allowing for minute modulations of its curvature and shape, [23] the results presented here show that, among others, decoration with increasingly larger side chains sacrifices the conformational uniqueness of the intramolecular seven-membered ring.…”

Electroactive Benzothiazole Hydrazones and Their [Mo6O19]2− Derivatives: Promising Building Blocks for Conducting Molecular Materials

“…[13] Inspired by the pioneering works of Hünig et al [14] and then Wheland, [15] some of us have started to explore the chemistry of 2,2'-azino-bis(N-alkylbenzothiazole) derivatives as an alternative donor. Thus, using the electrocrystallisation technique [16] with commercially available 2,2'-azino-bis(3-ethylbenzothiazole-6-sulfonate) (ABTS 2À ) and various cations, hybrid organic-inorganic molecular materials have been synthesised. [17][18][19] Recently, some interesting results on the electrocrystallisation of a selenium analogue, 2,2'-azino-bis(3-methylbenzoselenazole), have been reported.…”

Single-walled carbon nanotube-induced crystallinity on the electropolymeric film of tetraaminophthalocyaninatonickel(II) complex: Impact on the rate of heterogeneous electron transfer

“…To our knowledge, the induction of crystallinity by CNTs on polymers prepared by electrochemical techniques has not been reported, and we are not aware of any such observation for the electropolymerized films of metallophthalocyanine (MPc). As reviewed by Batail et al [20], the importance of electrocrystallization as an invaluable tool for the construction of ordered electroactive molecular solids cannot be over emphasized. Electrochemical synthesis of redox-active crystals on electrode surface may be exploited for the preparation of high-performance polycrystalline electrodes.…”