From 3D to 2D: Structural, Spectroscopic and Theoretical Investigations of the Dimensionality Reduction in the [PtAl2](delta-) Polyanions of the Isotypic MPtAl2 Series (M=Ca-Ba, Eu)

Author(s)

Stegemann, Frank ^[1] ; Block, Theresa ^[1] ; Klenner, Steffen ^[1] ; Zhang, Yuemei ^[2] ; Fokwa, Boniface P. T. ^[2] ; Timmer, Alexander ^[3] ; Moenig, Harry ^[3] ; Doerenkamp, Carsten ^[4] ; Eckert, Hellmut ^{[4, 5]} ; Janka, Oliver ^[1]

Affiliation

^[1] Westfalische Wilhelms Univ Munster, Inst Anorgan & Analyt Chem, Corrensstr 30, D-48149 Munster - Germany

^[2] Univ Calif Riverside, Dept Chem, 501 Box Springs Rd, Riverside, CA 92521 - USA

^[3] Westfalische Wilhelms Univ Munster, Phys Inst, Ctr Nano Technol CeNTech, Heisenbergstr 11, D-48149 Munster - Germany

^[4] Univ Sao Paulo, Inst Fis Sao Carlos, BR-13566590 Sao Carlos, SP - Brazil

^[5] Westfalische Wilhelms Univ Munster, Inst Phys Chem, Corrensstr 28, D-48149 Munster - Germany

• Document type: Journal article
• Source: CHEMISTRY-A EUROPEAN JOURNAL; v. 25, n. 45 JULY 2019.
• Web of Science Citations: 0

Abstract

Four new MPtAl2 (M=Ca, Sr, Ba, Eu) compounds, adopting the orthorhombic MgCuAl2-type structure, have been synthesized from the elements using tantalum ampoules. All compounds are obtained as platelet-shaped crystallites and exhibit an increasing moisture sensitivity with increasing size of the formal M cation. Structural investigations indicate a pronounced elongation of the crystallographic b-axis, which results in a significant distortion of the {[}PtAl2](delta-) polyanion. Within the polyanion, layer-like arrangements can be found with bonding Pt-Al interactions within the slab; the increase of the b-axis can be attributed to increasing Al-Al distances and therefore decreasing interactions between the slabs, caused by the differently-sized formal M cations. While the alkaline earth (M=Ca, Sr) representatives exhibit Pauli paramagnetism, BaPtAl2 shows diamagnetic behavior, finally EuPtAl2 is ferromagnetic with T-C=54.0(5) K. The effective magnetic moment indicates that the Eu atoms are in a divalent oxidation state, which is confirmed by Eu-151 Mossbauer spectroscopic investigations. Measurements below the Curie-temperature show a full magnetic hyperfine field splitting with B-hf=21.7(1) T. Al-27 and Pt-195 magic-angle spinning NMR spectroscopy corroborates the presence of single crystallographic sites for the Pt and Al atoms. The large Al-27 nuclear electric quadrupolar coupling constants confirm unusually strong electric field gradients, in agreement with the structural distortions and the respective theoretical calculations. X-ray photoelectron spectroscopy has been utilized to investigate the charge transfer within the polyanion. The Pt 4f binding energy decreases with decreasing electronegativity / ionization energy of the alkaline earth elements, suggesting an increasing electron density at the Pt atoms. Theoretical investigations underline the platinide character of the investigated compounds by Bader charge calculations. The analysis of the integrated crystal orbital Hamilton population (ICOHP) values, electron localization function (ELF) and isosurface analyses lead to a consistent structural picture, indicating stable layer-like arrangements of the {[}PtAl2](delta-) polyanion. (AU)

• FAPESP's process: 17/06649-0 - New Optical Materials based on Rare-Earth Doped Oxyfluoride Glasses and Ceramics: Structural Studies by Electron Paramagnetic Resonance Methods
• Grantee: Carsten Doerenkamp
• Support type: Scholarships in Brazil - Post-Doctorate