Solvent dependence of crystal morphology, donor/anion ratio and electrical conductivity in a series of hexagonal supramolecular organic conductors based on diiodo(pyrazino)tetrathiafulvalene (DIP)

Abstract

Themed issue: Halogen bonding: from self-assembly to materials and biomolecules COVER ARTICLEImakubo and Murayama Solvent dependence of crystal morphology, donor/anion ratio and electrical conductivity in a series of hexagonal supramolecular organic conductors based on diiodo(pyrazino)tetrathiafulvalene (DIP)

Unique Crystallization of Fullerenes: Fullerene Flowers

“…The lattice structure and morphology of a crystal often affect its properties, such as catalytic activity 1 , electrical conductivity 2 3 4 and photoluminescence 3 4 5 6 7 . Therefore, there has been considerable interest in the development of effective ways to grow crystals with controlled morphology.…”

2-Sulfanylidene-1,3-dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile

“…In addition, such contacts may lead to the formation of unique molecular networks which have special functions, such as inclusion properties (Yamashita & Tomura, 1998). Fused pyrazine units are expected to extend the -conjugated system, resulting in decreased Coulombic repulsion (Tomura & Yamashita, 1995;Belo et al, 2004;Nomura et al, 2009), and coordinate to transition metals (Imakubo et al, 2006;Rabaça & Almeida, 2010;Imakubo & Murayama, 2013), constructing organometallic coordination polymers. We report here the molecular and crystal structure of the title compound.…”

Use of Halogen Bonding in a Molecular Solid Solution to Simultaneously Control Spin and Charge

“…Supramolecular engineering strategies rely on noncovalent intermolecular interactions such as van der Waals interactions, coordination bonds, hydrogen bonds, and halogen bonds. Among them, the halogen bonds have attracted growing attention because of the highly directional nature and tunable bond strength, − and are utilized in a variety of fields such as anion recognitions, , drug design, − organic catalysts, − gel formation, molecular rotors, , phosphorescent materials, and conducting molecular materials. − …”

“…developed iodinated TTFs cation radical salts − including unique iodine-bonding networks between the donor and counteranion (donor···anion type) or among the donor molecules only (donor···donor type). The former type can give rise to novel physical properties such as superconductivity under uniaxial strain or at ambient pressure, and the latter type can give hexagonal supramolecular architecture with unique chemical recyclability and also controllability of the donor/anion ratio . Fourmigué et al found intriguing properties − including the competition between halogen bond and hydrogen bond and charge-assisted halogen bonding .…”

“…The former type can give rise to novel physical properties such as superconductivity under uniaxial strain 29 or at ambient pressure, 30 and the latter type can give hexagonal supramolecular architecture with unique chemical recyclability 31 and also controllability of the donor/anion ratio. 32 Fourmiguéet al found intriguing properties 33−37 including the competition between halogen bond and hydrogen bond 33 and chargeassisted halogen bonding. 34 Enoki et al reported anomalous magnetoresistance (MR) in π−d hybrid semiconductors based on brominated TTFs with magnetic anions FeX 4 − (X = Br, Cl), indicating an interaction between the donor and the anion.…”