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Title: Crystal and Magnetic Structures in Layered, Transition Metal Dihalides and Trihalides

Abstract

Materials composed of two dimensional layers bonded to one another through weak van der Waals interactions often exhibit strongly anisotropic behaviors and can be cleaved into very thin specimens and sometimes into monolayer crystals. Interest in such materials is driven by the study of low dimensional physics and the design of functional heterostructures. Binary compounds with the compositions MX 2 and MX 3 where M is a metal cation and X is a halogen anion often form such structures. Magnetism can be incorporated by choosing a transition metal with a partially filled d-shell for M, enabling ferroic responses for enhanced functionality. Here we give a brief overview of binary transition metal dihalides and trihalides, summarizing their crystallographic properties and long-range-ordered magnetic structures, focusing on those materials with layered crystal structures and partially filled d-shells required for combining low dimensionality and cleavability with magnetism.

Authors:
 [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1356933
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Crystals
Additional Journal Information:
Journal Volume: 7; Journal Issue: 5; Journal ID: ISSN 2073-4352
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; layered materials; van der Waals; monolayer; transition metal compounds; halides; crystal structure; magnetism; magnetic structure

Citation Formats

McGuire, Michael A. Crystal and Magnetic Structures in Layered, Transition Metal Dihalides and Trihalides. United States: N. p., 2017. Web. doi:10.3390/cryst7050121.
McGuire, Michael A. Crystal and Magnetic Structures in Layered, Transition Metal Dihalides and Trihalides. United States. doi:10.3390/cryst7050121.
McGuire, Michael A. Thu . "Crystal and Magnetic Structures in Layered, Transition Metal Dihalides and Trihalides". United States. doi:10.3390/cryst7050121. https://www.osti.gov/servlets/purl/1356933.
@article{osti_1356933,
title = {Crystal and Magnetic Structures in Layered, Transition Metal Dihalides and Trihalides},
author = {McGuire, Michael A.},
abstractNote = {Materials composed of two dimensional layers bonded to one another through weak van der Waals interactions often exhibit strongly anisotropic behaviors and can be cleaved into very thin specimens and sometimes into monolayer crystals. Interest in such materials is driven by the study of low dimensional physics and the design of functional heterostructures. Binary compounds with the compositions MX2 and MX3 where M is a metal cation and X is a halogen anion often form such structures. Magnetism can be incorporated by choosing a transition metal with a partially filled d-shell for M, enabling ferroic responses for enhanced functionality. Here we give a brief overview of binary transition metal dihalides and trihalides, summarizing their crystallographic properties and long-range-ordered magnetic structures, focusing on those materials with layered crystal structures and partially filled d-shells required for combining low dimensionality and cleavability with magnetism.},
doi = {10.3390/cryst7050121},
journal = {Crystals},
number = 5,
volume = 7,
place = {United States},
year = {Thu Apr 27 00:00:00 EDT 2017},
month = {Thu Apr 27 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 10works
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  • The He I protoelectron spectra of transition metal halide vapors MX/sub 2/ (M=Mn, Fe, Co, Ni; X=Cl, Br) are presented. The spectra are interpreted by comparing the experimental ionization energies with transition state eigenvalues calculated by the multiple scattering scheme, using a cellular (but not muffin tin) partitioning of space. Satisfactory correlation between theory and experiment is achieved when the calculations are carried out with spin-polarized orbitals. This correlation leads to the conclusion that the metal 3d orbitals contribute predominantly to the uppermost occupied orbitals for MnX/sub 2/, FeX/sub 2/, and CoX/sub 2/, but they are drawn deeper in NiX/submore » 2/ and become corelike orbitals at ZnX/sub 2/, the full d shell.« less
  • Six new transition metal(III) phosphites A{sup I}[V{sup III}(HPO{sub 3}){sub 2}], where A=K (1), NH{sub 4} (2) and Rb (3) and A{sup I}[Fe{sup III}(HPO{sub 3}){sub 2}] where A=K (4), NH{sub 4} (5) and Rb (6) have been synthesized under hydrothermal conditions and the solid-state structures were solved from single-crystal X-ray diffraction data. These compounds crystallize in the hexagonal system, space group P6{sub 3}mc (no. 186), with a=5.3294(2) A and c=12.3130(5) A for 1, a=5.3330(2) A and c=12.8760(4) A for 2, a=5.3459(2) A and c=12.6850(8) A for 3, a=5.3256(1) A and c=12.2362(3) A for 4, a=5.3229(2) A and c=12.8562(4) A for 5,more » a=5.3393(2) A and c=12.6913(5) A for 6, with Z=2 in the six phases. The crystal structures of these compounds are isotypic and exhibit a layered structure stacked along the c-axis with the A{sup +} cations located in the interlayer space. The [M{sup III}(HPO{sub 3}){sub 2}]{sup -} sheets are formed by MO{sub 6} octahedra interconnected by HPO{sub 3} tetrahedral phosphite oxoanions through sharing vertices. Thermal analysis shows a large range of stability for compounds containing potassium and rubidium cations with decomposition starting around 550 K for stable compounds and above 840 K for the most stable compounds leading in general to pyrophosphate compounds. Triangular nets of metallic centers are observed within the layers in which antiferromagnetic interactions are evidenced by magnetic susceptibility measurements suggesting magnetic frustration. - Graphical abstract: Six new transition metal(III) phosphites A{sup I}[M{sup III}(HPO{sub 3}){sub 2}], where A=K, NH{sub 4}, Rb and M=V, Fe, have been synthesized. The crystal structures of these compounds are isotypic and exhibit a lamellar structure related to Yavapaiite. The M(HPO{sub 3}){sub 2} layers separated by cationic species present the metallic centers in a triangular arrangement. Bulk antiferromagnetic behavior is observed for all the studied compounds. Highlights: Black-Right-Pointing-Pointer A new family of transition metal phosphites has been prepared. Black-Right-Pointing-Pointer The structure of these compounds is related to layered minerals like Yavapaiite. Black-Right-Pointing-Pointer Antiferromagnetic coupling is evidenced suggesting possible magnetic frustration. Black-Right-Pointing-Pointer Thermal studies show, in general, oxidation of phosphites into pyrophosphates.« less
  • Structural variations of the second- and third-row transition metal trihalides are rationalized via tight-binding band calculations and evaluation of Madelung energetic factors. The observed structure for a given metal halide is controlled by both the coordination geometry at the anion and the d electron configuration at the metal. As the polarizability of the halide increases, the M-X-M angle, in general, decreases so that three-dimensional frameworks occur for the fluorides, while layer and chain structures are found for the chlorides, bromides, and iodides. Within a particular halide system, systematic structural trends also occur as the d electron configuration changes. 56 refs.,more » 23 figs., 4 tabs.« less
  • A series of metal dicyanamide (dca) coordination polymers combined with cyanopyridine (cypy) terminal co-ligands, namely, [Co{sub 2}(dca){sub 4}(4-cypy){sub 4}] {sub n} (1), [Cd(dca){sub 2}(4-cypy){sub 2}] {sub n} (2), [Fe(dca){sub 2}(3-cypy){sub 2}] {sub n} (3) and [Co(dca){sub 2}(3-cypy){sub 2}] {sub n} (4), have been synthesized at the ambient conditions. X-ray single crystal diffraction reveals that complexes 1-4 have similar metal-dca coordination layers in which the octahedral metal centers are connected by {mu} {sub 1,5}-dca linkers. Notably, three types of 3-D packing lattices are observed for these layered arrays. The thermal stabilities of such new crystalline materials have been studied by thermogravimetricmore » analysis of mass loss. The magnetic properties of the Co{sup II} and Fe{sup II} complexes have been investigated and discussed in detail. A discrete mononuclear molecule [Cd(dca){sub 2}(pyom){sub 2}] (5) is also described, in which the chelated ligand O-methyl picolinimidate (pyom) arises from the addition of methanol solvent across the C{identical_to}N bond of 2-cypy. - Graphical abstract: A series of new metal dicyanamide complexes with cyanopyridine terminal co-ligands have been prepared and structurally determined by X-ray single-crystal diffraction. The magnetic properties of the Co{sup II} and Fe{sup II} layered coordination polymers are also discussed.« less
  • The electronic structures of the three layered transition metal-trichalcogenides NbSe{sub 3}, TaS{sub 3}, and TaSe{sub 3} were examined by performing tight-binding band electronic structure calculations. The Fermi surfaces of these materials were also calculated to analyze their metallic and/or charge density wave properties. In these trichalcogenides MX{sub 3} (M = Nb, Ta; X = S, Se) made up of prismatic MX{sub 3} chains, the broken X-X bonds of their equilateral-like MX{sub 3} chains and the short intra- and interlayer X{hor ellipsis}X contacts are found to be crucial for the semimetallic properties of TaSe{sub 3} and for the charge density wavemore » phenomena of NbSe{sub 3} and TaS{sub 3}. For the electronic parameters of the charge density waves in NbSe{sub 3} and TaS{sub 3} a quantitative agreement is obtained between the experimental observations and the present band electronic structure calculations. 29 refs., 9 figs., 3 tabs.« less