Effects of Solvent Additives on the Crystal Architecture of Supramolecular Conductors Based on Diiodo(ethylenedithio)tetraselenafulvalene and Indium Tetrahalide Anions

Abstract

Six new organic conductors were prepared on the basis of the iodine‐bonded π donor diiodo(ethylenedithio)tetraselenafulvalene and indium tetrahalide anions. The utilization of solvent additives made it possible to modify the quality, structure, morphology, and composition of the crystals. Among the additives, the addition of a few drops of water for the electrochemical crystallization induced the in situ transformation of the tetrahedral [InCl4]– anion to the octahedral [InCl4(H2O)2]– anion. Other small solvent molecules, such as methanol or ethanol, worked as well for the crystallization. All new salts include strong and directional iodine‐based halogen bonds, that is, the iodine bond, and the novel supramolecular structures are successfully tailored by characteristic intermolecular interaction. It is also worth noting that the tetrahedral geometry of the counteranion plays a key role in the construction of the solid‐crossing double‐layer structure of the donor molecules, which is observed in the newly prepared InCl4 and [InCl4(H2O)2] salts.

Cobaloximes as Building Blocks in Halogen-Bonded Cocrystals

“…As introducing metal atoms into a supramolecular material can significantly expand the possibilities of adding and controlling additional properties (such as magnetism and conductivity) [28,29], the use of halogen bonding in the crystal engineering of metal-organic materials has been an attractive challenge over the past decade [30][31][32][33][34][35][36][37][38][39][40]. While there have been substantial studies into halogen bonding in single component metal-organic solids [30][31][32][33][34][35][36][37][38][39][40][41], synthesis of multi-component materials based on halogen-bonded metal-organic components has been receiving much less attention. Particularly scarce are studies involving cocrystals of neutral metal-organic components acting as halogen bond acceptors [42][43][44][45][46][47].…”

Exploring the Halogen-Bonded Cocrystallization Potential of a Metal-Organic Unit Derived from Copper(ii) Chloride and 4-Aminoacetophenone

“…A number of reports and reviews have been published dealing with halogen bonding in single component metal-organic solids [15][16][17][20][21][22][23]. Most systematic studies of multicomponent metal-organic materials have focused on the utilization of halogen bonding with halide and pseudohalide (CN − , SCN − , OCN − , and similar) ligands and ions, as they have shown to be reliable in the synthesis of ionic metal-organic materials [24][25][26][27][28][29][30][31][32][33] and metal-organic cocrystals [15,[34][35][36]. Several promising alternative approaches to obtaining neutral metal-organic materials have also recently been presented, generally focused on cocrystallizing neutral halogen bond donors with metal complex subunits that have either large chelating ligands (such as imines [37,38], acetylacetonates [39,40], or pyridine derivatives [41]) with pendant acceptor groups, or neutral monodentate ligands such as morpholine or thiomorpholine [42] coordinated to the metal complex.…”

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. − …”

“…One of the authors (T.I.) 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 .…”