Water‐Induced Breaking of the Coulombic Ordering in a Room‐Temperature Ionic Liquid Metal Complex

Abstract

Control of ion arrangements in ionic liquids represents a major challenge owing to the presence of the predominant coulombic interactions between cationic and anionic ion species that forms the coulombic ordering. Here, water‐induced ion rearrangement in a room‐temperature ionic liquid (RT‐IL) metal complex, (1‐ethyl‐3‐methylimidazolium)2[MnN(CN)4], is demonstrated through coordinative interactions between anions. Solidification occurred, which was associated with the formation of a “separated” structure consisting of cation columns and anionic cyanide‐bridged one‐dimensional coordination polymers. The energy diagram is in accord with the resultant RT‐IL incorporating mononuclear [MnN(CN)4]2− molecules being a kinetic phase stabilized by inter‐ion repulsions of the anionic divalent metal complex moieties. Water acts to decrease the coulombic interactions, including repulsion, giving rise to breaking of the coulombic ordering arising from coordination bond formation in the IL phase.

Vapor-Induced Conversion of a Centrosymmetric Organic–Inorganic Hybrid Crystal into a Proton-Conducting Second-Harmonic-Generation-Active Material

“…We synthesized 1 via an ionic exchange method , using (PPh 4 ) 2 [MnN­(CN) 4 ]·2H 2 O and NEt 4 ClO 4 and subjected it to a single-crystal X-ray structural analysis at 298 K (Figure a and Table S1). 1 crystallized in the tetragonal centrosymmetric space group P 4/ ncc .…”

“…We synthesized 1 via an ionic exchange method 41,42 1a and Table S1). 1 crystallized in the tetragonal centrosymmetric space group P4/ncc.…”

Strongly Enhanced Polarization in a Ferroelectric Crystal by Conduction-Proton Flow

“…In this study, 1•H 2 O was synthesized by an ion-exchange method 37,38 1 and Table S1). Furthermore, the anisotropic 1D assemblies of the [MnN(CN) 4 ] 2− units were formed by the nitrido bridges between the Mn centers with a bond distance of 2.389(9) Å.…”

“…In this study, 1·H 2 O was synthesized by an ion-exchange method , using (PPh 4 ) 2 [MnN­(CN) 4 ]·2H 2 O and KBPh 4 . Single crystals of 1·H 2 O were obtained by recrystallization from MeOH, after which 1·H 2 O was crystallized in orthorhombic space group Imm 2 at 100 K (Figure and Table S1).…”

Revisiting the carbon mesopore contribution towards improved performance of ionic liquid–based EDLCs at sub-zero temperatures

“…Difference in the pore size can affect the capacitance performance as well as the rate capability of the carbon-based energy storage devices [11]. While the neat ILs form long-range layered structures along the pore wall under the charge overscreening, the ionic order in these ILs can be disturbed either with a solvent [12] or by using IL binary mixtures taking benefit from the absence of crystallization due to the difference in ion size; e.g., the cations do not fit into the anionic lattice and/or the anions do not completely participate in the crystal structure [7]. Overall, the factors such as presence of small ordered pores facilitate in creating a so-called superionic state (where image charge drives easier packing of ions with the same sign) [13,14].…”