Orbital Contribution to Paramagnetism and Noninnocent Thiophosphate Anions in Layered Li2MP2S6 Where M = Fe and Co
journal contributionposted on 07.07.2021, 13:33 by Timothy J. Diethrich, Peter Y. Zavalij, Stephanie Gnewuch, Efrain E. Rodriguez
Transition-metal thiophosphates and selenophosphates are layered systems with the potential for displaying two-dimensional (2D) magnetic phenomena. We present the crystal structures and magnetic properties of two lithium transition-metal thiophosphates, Li1.56Co0.71P2S6 and Li2.26Fe0.94P2S6. The previously unreported Li1.56Co0.71P2S6 crystallizes in the trigonal space group P31m with lattice parameters a = 6.0193(6) Å and c = 6.5675(9) Å. The CoS6 octahedra are arranged in a honeycomb lattice and form 2D layers separated by lithium cations. The previously solved Li2.26Fe0.94P2S6 is isostructural to Li1.56Co0.71P2S6 but displays site mixing between the Li+ and Fe2+ cations within the thiophosphate layer. Unusually, Li1.56Co0.71P2S6 appears to have P2S63– and not P2S64– anions. We therefore term it a “noninnocent” anion because of the ambiguous nature of its oxidation state. Combined neutron diffraction and magnetization measurements reveal that both Li1.56Co0.71P2S6 and Li2.26Fe0.94P2S6 display magnetic anisotropy as well as no long-range magnetic order down to 5 K. In the iron thiophosphate, susceptibility indicates an effective moment of 5.44(3) μB, which may be best described by an S + L model, where S = 2 and L = 2, or close to the free ion limit. In the cobalt thiophosphate, we found the effective moment to be 4.35(2) μB, which would point to an S = 3/2 and L = 1 model due to octahedral crystal-field splitting.
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Li 2.26 Fe 0.94 P 2 S 6 displayLi 1.56 Co 0.71 P 2 S 6 crystallizesLayered Li 2 MP 2 S 6form 2 D layersCoS 6 octahedraion limitLi 2.26 Fe 0.94 P 2 S 6lithium transition-metal thiophosphatesL modelmagnetization measurementsiron thiophosphateÅ.Co Transition-metal thiophosphateslithium cationsdisplays sitespace group P 31 m1 model5 KLi 1.56 Co 0.71 P 2 S 6Orbital Contributionoctahedral crystal-field splittingcrystal structuresNoninnocent Thiophosphate Anionsthiophosphate layerhoneycomb latticeneutron diffractionlattice parameterscobalt thiophosphateoxidation state