X-ray absorption spectroscopy insights on the structure anisotropy and charge transfer in Chevrel Phase chalcogenides

Hyler, Forrest P.; A., Wuille Bille, Brian; Ortiz-Rodríguez, Jessica C.; Sanz-Matı́as, Ana; Roychoudhury, Subhayan; Perryman, Joseph T.; Patridge, Christopher J.; Singstock, Nicholas R.; Musgrave, Charles B.; Velázquez, Jesús M.

doi:10.1039/d1cp04851a

Cited by 3 publications

(1 citation statement)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This expected orthogonal trend is consistent with our expectation that the q-1D nature of the lattice can compensate for anisotropic expansion/ contraction across the various axes in the crystal. We anticipate that this anisotropic lattice modulation induced by surface alkyl ammonium substitution could also impose an atomic-level anisotropy in the local coordination environment of Mo that comprise the [Mo 6 Te 6 ] n − chains, as was comprehensively reported in Mo-based Chevrel clusters, 71 albeit less pronounced. Probing this, however, would require either highresolution diffraction techniques or a detailed X-ray absorption spectroscopy analysis which are beyond the scope of this current study.…”

Section: Resultsmentioning

confidence: 66%

Functionalization and Structural Evolution of Conducting Quasi-One-Dimensional Chevrel-Type Telluride Nanocrystals

Ogura,

Cordova,

Aoki

et al. 2024

Chem. Mater.

View full text Add to dashboard Cite

Interfacing organic molecular groups with well-defined inorganic lattices, especially in low dimensions, enables synthetic routes for the rational manipulation of both their local or extended lattice structures and physical properties. While appreciably studied in two-dimensional systems, the influence of surface organic substituents on many known and emergent one-dimensional (1D) and quasi-1D (q-1D) crystals has remained underexplored. Herein, we demonstrate the surface functionalization of bulk and nanoscale Chevrel-like q-1D ionic crystals using In 2 Mo 6 Te 6 , a predicted q-1D Dirac semimetal, as the model phase. Using a series of alkyl ammonium (−NR 4 + ; R = H, methyl, ethyl, butyl, and octyl) substituents with varying chain lengths, we demonstrate the systematic expansion of the intrachain c-axis direction and the contraction of the interchain a/b-axis direction with longer chain substituents. Additionally, we demonstrate the systematic expansion of the intrachain c-axis direction and the contraction of the interchain a/b-axis direction as the alkyl chain substituents become longer using a combination of powder X-ray diffraction and Raman experiments. Beyond the structural modulation that the substituted groups can impose on the lattice, we also found that the substitution of ammonium-based groups on the surface of the nanocrystals resulted in selective suspension in aqueous (NH 4 + -functionalized) or organic solvents (NOc 4 +functionalized), imparted fluorescent character (Rhodamine B-functionalized), and modulated the electrical conductivity of the nanocrystal ensemble. Altogether, our results underscore the potential of organic−inorganic interfacing strategies to tune the structural and physical properties of rediscovered Chevrel-type q-1D ionic solids and open opportunities for the development of surface-addressable building blocks for hybrid electronic and optoelectronic devices at the nanoscale.

show abstract

Section: Resultsmentioning

confidence: 66%

Functionalization and Structural Evolution of Conducting Quasi-One-Dimensional Chevrel-Type Telluride Nanocrystals

Ogura,

Cordova,

Aoki

et al. 2024

Chem. Mater.

View full text Add to dashboard Cite

show abstract

Unleashing the Potential of Fast Charging Batteries: Leveraging Anion Redox Chemistry in Ni- and Co-Free Cathodes

Nagarajan,

Roychoudhury,

Weiland

et al. 2024

Chem. Mater.

View full text Add to dashboard Cite

Exploring Charge Redistribution at the Cu/Co₆Se₈ Interface

Krajewski,

Love,

Kephart

et al. 2024

Inorg. Chem.

View full text Add to dashboard Cite

This study investigates the electronic interactions and charge redistribution at the dopant−support interface using a Cu/Co 6 Se 8 cluster construct. Specifically, the redox cluster series [Cu 3 Co 6 Se 8 L 6 ] n ([1-Cu 3 ] n ; n = 0, −1, −2, −3; L = Ph 2 PNTol − , Ph = phenyl, Tol = p-tolyl) spanning four distinct oxidation states is synthesized and characterized using a multitude of techniques, including multinuclear NMR, UV−vis, XANES, and X-ray crystallography. Structural investigations indicate that the clusters are isostructural and chiral, adopting a pseudo-D 3 symmetry. Paramagnetic 31 P NMR spectroscopy and solution-phase magnetic measurements together with DFT calculations are employed to interrogate the electronic structure and spin-state changes across the [1-Cu 3 ] 3− to 1-Cu 3 redox series, revealing that the copper edge sites retain a +1 oxidation state while the Co/Se core becomes increasingly oxidized, yielding a highly zwitterionic cluster.

show abstract

X-ray absorption spectroscopy insights on the structure anisotropy and charge transfer in Chevrel Phase chalcogenides

Abstract: The electronic structure and local coordination of binary (Mo6T8) and ternary Chevrel Phases (MxMo6T8) are investigated for a range of metal intercalant and chalcogen compositions. We evaluate differences in the...

Cited by 3 publications

References 32 publications

Functionalization and Structural Evolution of Conducting Quasi-One-Dimensional Chevrel-Type Telluride Nanocrystals

Functionalization and Structural Evolution of Conducting Quasi-One-Dimensional Chevrel-Type Telluride Nanocrystals

Unleashing the Potential of Fast Charging Batteries: Leveraging Anion Redox Chemistry in Ni- and Co-Free Cathodes

Exploring Charge Redistribution at the Cu/Co₆Se₈ Interface

Contact Info

Product

Resources

About

X-ray absorption spectroscopy insights on the structure anisotropy and charge transfer in Chevrel Phase chalcogenides

Abstract: The electronic structure and local coordination of binary (Mo6T8) and ternary Chevrel Phases (MxMo6T8) are investigated for a range of metal intercalant and chalcogen compositions. We evaluate differences in the...

Cited by 3 publications

References 32 publications

Functionalization and Structural Evolution of Conducting Quasi-One-Dimensional Chevrel-Type Telluride Nanocrystals

Functionalization and Structural Evolution of Conducting Quasi-One-Dimensional Chevrel-Type Telluride Nanocrystals

Unleashing the Potential of Fast Charging Batteries: Leveraging Anion Redox Chemistry in Ni- and Co-Free Cathodes

Exploring Charge Redistribution at the Cu/Co6Se8 Interface

Contact Info

Product

Resources

About

Exploring Charge Redistribution at the Cu/Co₆Se₈ Interface