Facile and rapid synthesis of crystalline quadruply bonded Cr(ii) acetate coordinated with axial ligands.

A quadruple bond formed between d-block or f-block atoms is an interesting research topic due to its unique nature including a supershort bonding distance and narrow energy gap between δ and δ*. Among various multiply bonded complexes, quadruply bonded Cr(ii) acetates are considered useful to control the δ-δ* energy gap by the Lewis basicity of additional ligands. However, the synthesis and preparation of the high-quality, large-sized crystals of Cr(ii) acetates coordinated with axial ligands (Cr2(OAc)4L2) have been difficult due to their vulnerability to O2, a representative oxidizing agent under aerobic conditions. In this study, we report a facile synthesis of sub-millimeter-scale crystals of Cr2(OAc)4L2 by simple dissolution of Cr2(OAc)4 in ligand solvents L. To obtain stably ligated Cr2(OAc)4L2, anhydrous Cr(ii) acetates (Cr2(OAc)4) were dissolved in the ligand solvents L, which was degassed of dissolved O2. Also, sub-millimeter-scale single crystals of Cr2(OAc)4L2 were produced rapidly for less than an hour by the drop-drying process. The single-crystalline phase of the synthesized Cr(ii) complexes was measured by X-ray diffraction techniques, confirming the dependency of Lewis basicity of the additional axial ligands on the Cr-Cr quadruple bond distance. Further, the Raman peaks of the quadruple bonds in Cr2(OAc)4L2 were observed to be red-shifted with the increased basicity of the axial ligands.

Crystallinity-dependence of ionic conductivity in the ion pairs of a multi-interactive anion.

Ammonium and sodium salts (ion pairs) of a multi-interactive tri(4-pyridyl)hexaazaphenalenyl anion (TPHAP(-)) showed completely different ion-conductive properties depending on the crystal structure. TPHAP columnar crystals showed a high conductivity of 10(-3) S cm(-1) while retaining their structures even under humid conditions, whereas TPHAP dimer crystals exhibited a conductivity of ∼10(-5) S cm(-1) with crystallinity deterioration. The main unit structures induced by multi-interactivity realized different water accessibility, which explains the differences in their ion conductivity and stability against humidity.