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1.
Adv Mater ; 35(12): e2207121, 2023 Mar.
Article in English | MEDLINE | ID: mdl-36642840

ABSTRACT

Magnetic semimetals have increasingly emerged as lucrative platforms hosting spin-based topological phenomena in real and momentum spaces. Cr1+ δ Te2 is a self-intercalated magnetic transition metal dichalcogenide (TMD), which exhibits topological magnetism and tunable electron filling. While recent studies have explored real-space Berry curvature effects, similar considerations of momentum-space Berry curvature are lacking. Here, the electronic structure and transport properties of epitaxial Cr1+ δ Te2 thin films are systematically investigated over a range of doping, δ (0.33 - 0.71). Spectroscopic experiments reveal the presence of a characteristic semi-metallic band region, which shows a rigid like energy shift with δ. Transport experiments show that the intrinsic component of the anomalous Hall effect (AHE) is sizable and undergoes a sign flip across δ. Finally, density functional theory calculations establish a link between the doping evolution of the band structure and AHE: the AHE sign flip is shown to emerge from the sign change of the Berry curvature, as the semi-metallic band region crosses the Fermi energy. These findings underscore the increasing relevance of momentum-space Berry curvature in magnetic TMDs and provide a unique platform for intertwining topological physics in real and momentum spaces.

2.
Inorg Chem ; 61(5): 2428-2443, 2022 Feb 07.
Article in English | MEDLINE | ID: mdl-35084833

ABSTRACT

The reaction of mid to late lanthanide ions with the N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromobenzyl)ethylene-diamine organic ligand and monolacunary Keggin type [α-SiW11O39]8- anion affords a series of isostructural compounds, namely, K5[LnIII(α-SiW11O39)(C20H22Br2N2O4)]·14H2O (1-Ln, Ln = Sm to Lu). The molecular structure of these sandwich-type complexes is formed by the LnIII ion in a biaugmented trigonal prismatic geometry, which occupies the external O4 site of the organic ligand and the vacant site of the lacunary polyoxometalate (POM) unit. The empty N2O2 coordination site of the organic ligand allows its unprecedented folding, which displays a relative perpendicular arrangement of aromatic groups. Weak Br···Br and π-π interactions established between adjacent molecular units govern the crystal packing, which results in the formation of assemblies containing six hybrid species assembled in a chairlike conformation. 1-Gd and 1-Yb display slow relaxation of the magnetization after the application of an external magnetic field with maxima in the out-of-phase magnetic susceptibility plots below ∼5-6 K, which is ascribed to the presence of various relaxation mechanisms. Moreover, photoluminescent emission is sensitized for 1-Sm and 1-Eu in the visible region and 1-Er and 1-Yb in the NIR. In contrast, the quenching of metal-centered luminescence in the 1-Tb derivative has been attributed to the out-of-pocket coordination mode of the lanthanide center within the POM fragment. It is demonstrated that the 1-Yb dual magneto-luminescent material represents the first lanthanide-containing POM reported to date with simultaneous slow magnetic relaxation and NIR emission. Solution stability of the hybrid molecular species in water is also confirmed by ESI-mass spectrometry experiments carried out for 1-Tb and 1-Tm.

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