Intercalation on Transition Metal Trichalcogenides via a Quasi-Amorphous Phase with 1D Order

Intercalation into 1D transition metal trichalcogenides (TMTs) in which fibers are bonded by a weak van der Waals force can be expected to create various intercalation compounds and develop unique physical properties according to the combination of the host materials and guest ions. However, structural changes via intercalation into 1D TMTs are not as simple as those in 2D transition metal dichalcogenides (TMDs) and are still not understood comprehensively. ZrTe₃: a typical compound with a 1D trigonal prismatic structure, belongs to TMTs. Herein, through the Ag introduction to ZrTe₃ via solid-state intercalation, a novel crystal phase with a 1D octahedral structure and a quasi-amorphous (QA) phase during the structural transition are discovered; the QA phase is a novel state of matter in which long-range order is lost while retaining 1D order. Based on the Ag concentration, the transport properties are flexibly modulated from superconductivity to semiconductivity. Density functional theory calculations indicate the attraction between Ag ions and the pair diffusion due to their attraction. Furthermore, judging the attraction or repulsion between guest ions predicts whether to induce a QA phase or simple lattice expansion like the intercalation into 2D TMDs.     

Iridium‐Catalyzed [2+2+2] Cycloaddition of α,ω‐Diynes with Cyanamides

The complex [Ir(cod)Cl]₂/DPPF or rac‐BINAP is an efficient catalyst for the [2+2+2] cycloaddition of α,ω‐diynes with cyanamides. A wide range of cyanamides derived from secondary amines are good coupling partners for α,ω‐diynes. The reaction of unsymmetrical α,ω‐diynes possessing two different internal alkyne moieties with cyanamides is regioselective. A competitive experiment showed that cyanamide is more reactive than nitrile. This higher reactivity of cyanamide than nitrile was analyzed based on density functional theory (DFT) calculations at the B3LYP level.