Inductive-Effect-Driven Tunability of Magnetism and Luminescence in Triangular Layers ANd(SO4)2 (A = Rb, Cs)
Xudong Huai1, Ebube Oyeka1, Uchenna Chinaegbomkpa1
1Department of Chemistry, Clemson University, Clemson, South Carolina 29634, United States.
None:
Tuning the energy landscape of many-body electronic states in extended solids through the inductive effect─a concept widely used in organic chemistry─offers a new, effective strategy for materials development. Here, we demonstrate this approach using the ANd(SO4)2 (A = Rb, Cs) model system, which possesses different A-site electronegativity and displays a distorted triangular lattice of Nd3+ (4I9/2 ground term). Magnetization data indicate appreciable antiferromagnetic interactions without long-range ordering down to 1.8 K while highlighting the tunable population of the electronic states. Temperature-dependent and time-resolved photoluminescence measurements reveal that emissions and nonradiative processes can be modified by the inductive effect at the atomic level. Heat capacity data confirm no magnetic ordering and add insight into the role of phonons in emission lifetime. Density functional theory calculations support enhanced covalency in the Cs compound compared to the Rb counterpart while acknowledging the adjustable magnetic intralayer and interlayer exchange pathways. These results demonstrate a viable framework for utilizing the inductive effect as an important knob for simultaneously dialing in magnetic, optical, and electronic properties in quantum materials.
Related Concept Videos
03:02Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
02:42Valence Bond Theory
02:58Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
02:42Ionic Crystal Structures
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...