A complex salt of tetraethylammonium cations and anions consisting of an inorganic {V 4 O 8 } core chelated with l -tartaric acid undergoes structural transformations triggered by changes in humidity and temperature, giving rise to switchable properties.
Magnetism and sensory properties reflect structural changes in cinchonine–chloro–cobalt( ii ) compounds induced by the action of small solvent molecules in two ways: vapour phase exposure or post-synthetic mechanochemical modification.
Due to soft crystal packing driven by non-covalent interactions 3-quinuclidinone cations and (CoCl4)2– anions self-assemble along the preferred crystallographic orientation and form homogeneous thin films with switchable ferroelectric properties.
This study examines the influence of ligand design on the structural, optical, and electrical properties of copper-based coordination complexes. Ligands H2L1 and H2L2 were synthesized via the reaction of 5-nitrosalicylaldehyde with 2-hydroxy- or 4-hydroxybenzhydrazide. H4L3 was obtained from the reaction of carbohydrazide and salicylaldehyde, while H4L4 was prepared by condensing 4-methoxysalicylaldehyde with thiocarbohydrazide. The research focuses on two key design elements: (1) the effect of hydroxyl group positioning on the aroyl ring in hydrazide ligands (H2L1 vs. H2L2) and (2) the impact of carbonyl versus thiocarbonyl groups and aldehyde substituents in hydrazone ligands (H4L3 vs. H4L4). The resulting complexes, [Cu2(L1)2], [Cu2(L2)2(MeOH)3], [Cu2(L3)(H2O)2], and [Cu2(L4)(H2O)2], were synthesized and characterized using attenuated total reflectance infrared (IR-ATR) spectroscopy, thermogravimetric analysis (TG), and UV-Vis diffuse reflectance spectroscopy. Their electrical properties were investigated using solid-state impedance spectroscopy (IS). The crystal and molecular structure of the complex [Cu2(L2)2(MeOH)3]∙MeOH was determined by single-crystal X-ray diffraction (SCXRD). This study underscores the pivotal role of ligand modifications in modulating the functional properties of coordination complexes, offering valuable insights for the advancement of materials chemistry.
The synthesis of a homochiral building block based on L-tartrate-chromium(III) complex anions is reported. The dinuclear complex anion, which contains two bridging L-tartrate ligands and one aromatic N-donor ligand coordinated to chromium(III) ions, exhibits a boat conformation in which intramolecular resonance-assisted hydrogen bonding is present. The sodium L-tartrate-chromium(III) compound with the formula Na[Cr2(bpy)2(L-tart)2H]·9H2O (1) crystallizes from a methanol–water solution as a high water content material in the monoclinic space group P2. The as-synthesized compound is only stable at high relative humidity and undergoes structural transformations during drying, which are accompanied by water loss. However, these transformations are reversible and upon wetting, the material returns to its high water content structure. Based on a combination of experimental techniques (PXRD, in situ ATR-FTIR and EPR spectroscopy), the structure of the complex anions appears to be insensitive to the humidity variable processes (wetting and drying). Due to the presence of several hydrogen acceptor and donor groups in the L-tartrate-chromium(III) complex anion, we investigated the proton transport properties of a sodium L-tartrate-chromium(III) compound by impedance spectroscopy under dry and wet conditions at different temperatures. Since the relative humidity affects the structural transformations in this system, it also has a large influence on the proton conductivity, which varies by up to four orders of magnitude depending on the degree of hydration. These results confirm that the proton conductivity can be tuned in flexible structures in which non-covalent interactions determine the crystal packing.
Reduction of zeolite particles size leads to a shift in the proton transfer mechanism from the vehicular mechanism through zeolite channels to the energetically more favourable Grotthuss mechanism of the surface adsorbed water layers.