We present comprehensive measurements of the structural, magnetic and electronic properties of layered van-der-Waals ferromagnet VI3 down to low temperatures. Despite belonging to a wellstudied family of transition metal trihalides, this material has received very little attention. We outline, from high-resolution powder x-ray diffraction measurements, a corrected room-temperature crystal structure to that previously proposed and uncover a structural transition at 79 K, also seen in the heat capacity. Magnetization measurements confirm VI3 to be a hard ferromagnet (9.1 kOe coercive field at 2 K) with a high degree of anisotropy, and the pressure dependence of the magnetic properties provide evidence for the two-dimensional nature of the magnetic order. Optical and electrical transport measurements show this material to be an insulator with an optical band gap of 0.67 eV -the previous theoretical predictions of d-band metallicity then lead us to believe VI3 to be a correlated Mott insulator. Our latest band structure calculations support this picture and show good agreement with the experimental data. We suggest VI3 to host great potential in the thriving field of low-dimensional magnetism and functional materials, together with opportunities to study and make use of low-dimensional Mott physics.Two-dimensional van-der-Waals (vdW) magnetic materials have in recent years become the subject of a wide range of intense research 1 . While a large portion of research into two-dimensional materials has centered on graphene, the addition of magnetism into such a system leads to many interesting fundamental questions and opportunities for device applications 2-6 . Particularly for future spintronics applications, semiconducting or metallic materials which exhibit ferromagnetism down to monolayer thickness are an essential ingredient. This has led to a large volume of recent publications on two-dimensional honeycomb ferromagnet CrI 3 7-12 . CrI 3 and VI 3 belong to a wider family of MX 3 transition metal trihalides, with X = Cl, Br, I, which were synthesized in the 60s 13,14 but have since seen little interest until recently 15 . VI 3 is an insulating two-dimensional ferromagnet with a Curie Temperature, T c , given as 55 K and reported to have the layered crystal structure of BiI 3 with space group R-3 [16][17][18] . As shown in a recent review 15 , there is very little available information on VI 3 other than the structure and the expected S = 1 from the 3d 2 configuration of the vanadium sites. Calculations using density functional theory, which additionally yield the exchange constants, have suggested VI 3 to not only remain ferromagnetic down to a single crystalline layer, but to also exhibit Dirac half-metallicity, of interest for spintronic applications 19 .In these vdW materials, hydrostatic pressure forms an extremely powerful tuning parameter. Given the weak mechanical forces between the crystal planes, the application of pressure will dominantly have the effect of pressing the ab planes together, and gradually an...

Two-dimensional materials have proven to be a prolific breeding ground of new and unstudied forms of magnetism and unusual metallic states, particularly when tuned between their insulating and metallic phases. In this paper we present work on a new metal to insulator transition system FePS3 . This compound is a two-dimensional van-der-Waals antiferromagnetic Mott insulator. Here we report the discovery of an insulator-metal transition in FePS3, as evidenced by x-ray diffraction and electrical transport measurements, using high pressure as a tuning parameter. Two structural phase transitions are observed in the x-ray diffraction data as a function of pressure and resistivity measurements show evidence of the onset of a metallic state at high pressures. We propose models for the two new structures that can successfully explain the x-ray diffraction patterns.

The phosphinidene-bridged complex [Mo2Cp2(μ-PR*)(CO)4] (R = 2,4,6- C6H2 tBu3) experiences an intramolecular C−H bond cleavage from a tBu group to give the phosphide-hydride derivative [Mo2Cp2(μ-H){μ-P(CH2CMe2)C6H2 tBu2}(CO)4] in refluxing diglyme (ca. 438 K) or under exposure to near-UV−visible light. In contrast, its exposure to UV light yields two different dicarbonyl derivatives depending on the reaction conditions, either the triply bonded [Mo2Cp2(μ-PR*)(μ-CO)2] (Mo−Mo = 2.5322(3) Å) or its isomer [Mo2Cp2(μ-κ 1:κ 1,η 6-PR*)(CO)2], in which the phosphinidene ligand bridges asymmetrically the metal centers while binding its aryl group to one of the molybdenum atoms in a η6-fashion. The latter complex experiences a proton-catalyzed tautomerization to yield the cyclopentadienylidene−phosphinidene derivative [Mo2Cp(μ-κ 1:κ 1,η 5-PC5H4)(η 6-R*H)(CO)2]. Carbonylation of the η 6-phosphinidene complex proceeds stepwise through the η 4-tricarbonyl complex [Mo2Cp2(μ-κ 1:κ 1,η 4-PR*)(CO)3] and then to the starting tetracarbonyl compound, whereas its reaction with CNtBu yields only the η 4-complex [Mo2Cp2(μ-κ 1:κ 1,η 4-PR*)(CNtBu)(CO)2], which was characterized through an X-ray study. The η 4-tricarbonyl species reacts with CNtBu in tetrahydrofuran to give the metal−metal bonded derivative [Mo2Cp2(μ-PR*)(CNtBu)(CO)3]. In petroleum ether, however, this reaction yields the bis(isocyanide) derivative [Mo2Cp2(μ-PR*)(CNtBu)2(CO)3], which has an asymmetric trigonal phosphinidene bridge and no metal−metal bond. All the above results can be explained by assuming the operation of two primary processes in the photolysis of [Mo2Cp2(μ-PR*)(CO)4], one of them involving a valence tautomerization of the phosphinidene ligand, from the trigonal (four-electron donor) to the pyramidal (two-electron donor) coordination mode. The carbonylation reaction of the η 6-complex is accelerated by the presence of CuCl, due to the formation of the trimetal species [CuMo2(Cl)Cp2(μ-κ 1:κ 1:κ 1,η 6-PR*)(CO)2] and [CuMo2(Cl)Cp2(μ-κ 1:κ 1:κ 1,η 4-PR*)(CO)3]. The latter complexes were also characterized by single-crystal X-ray studies.