RESEARCH ARTICLE 1 Ln2SeO 32SO 4H 2O2 Ln Sm Dy Yb A Mixed -Ligand Pathway

2025-04-29 0 0 2.05MB 9 页 10玖币
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RESEARCH ARTICLE
1
Ln2(SeO3)2(SO4)(H2O)2 (Ln = Sm, Dy, Yb): A Mixed-Ligand Pathway
to New Lanthanide(III) Multifunctional Materials Featuring Nonlinear
Optical and Magnetic Anisotropy Properties
Ebube E. Oyeka,[a] Michał J. Winiarski,[b] Hanna Świątek,[b] Wyatt Balliew,[a] Colin D. McMillen,[a]
Mingli Liang,[c] Maurice Sorolla II,[d] and Thao T. Tran*[a]
[a] E.E. Oyeka, W. Balliew, Dr. C. D. McMillen, Prof. T.T. Tran
Department of Chemistry,
Clemson University,
Clemson, SC 29630, United States
E-mail: thao@clemson.edu
[b] Prof. M. J. Winiarski, H. Świątek
Faculty of Applied Physics and Mathematics and Advanced Materials Center,
Gdansk University of Technology, ul
Narutowicza 11/12, 80-233 Gdansk, Poland
[c] Dr. M. Liang
Department of Chemistry,
University of Houston,
Houston, TX 77204, United States
[d] Prof. M. Sorolla II
Department of Chemical Engineering,
University of the Philippines Diliman,
Quezon City 1101, Philippines
Abstract: Bottom-up assembly of optically nonlinear and magnetically
anisotropic lanthanide materials involving precisely placed spin carriers
and optimized metal-ligand coordination offers a potential route to
developing electronic architectures for coherent radiation generation
and spin-based technologies, but the chemical design historically has
been extremely hard to achieve. To address this, we developed a
worthwhile avenue for creating new noncentrosymmetric chiral Ln3+
materials Ln2(SeO3)2(SO4)(H2O)2 (Ln = Sm, Dy, Yb) by mixed-ligand
design. The materials exhibit phase-matching nonlinear optical
responses, elucidating the feasibility of the heteroanionic strategy.
Ln2(SeO3)2(SO4)(H2O)2 displays paramagnetic property with strong
magnetic anisotropy facilitated by large spin-orbit coupling. This study
demonstrates a new chemical pathway for creating previously unknown
polar chiral magnets with multiple functionalities.
Introduction
Lanthanide materials, exhibiting diverse physical responses when
subjected to external stimuli, are at the forefront of recent
technological advances in optical frequency conversion, quantum
computing and spintronics.[1] Nonlinear optical lanthanide
compounds are promising for improved second-harmonic
generation (SHG) efficiencies and wide transparency window owing
to the relatively large hyperpolarizability of Ln-based distorted
polyhedra and the narrow bandwidth between the f orbitals of Ln3+
and the s and p orbitals of anions.[2] SHG phenomena occur in
noncentrosymmetric (NCS) materials in which spatial inversion
center symmetry is broken.[3] Paramagnetic Ln3+ materials possess
a large orbital magnetic moment and strong spin-orbit coupling
associated with f orbitals, yielding high magnetic anisotropy.[1c, 4] In
addition, the “buried” nature of the 4f orbitals, which is attributed to
the lanthanide contraction, in tandem with their poor overlap with 5d
orbitals give rise to a smaller magnitude of the ligand-field-induced
spitting than that of spin-orbit coupling.[5] As a result, the electronic
and magnetic properties of lanthanides are mostly driven by large
spin-orbit coupling, a phenomenon known to facilitate unique
physical behaviors such as magnetic skyrmions, multiferroicity,
quantum spin liquids, and topological states of matter.[1e, 6] Despite
the impressive progress in separately investigating optical and
magnetic functionalities of Ln3+ materials, significant barriers remain
as to how optical and magnetic properties can be harmonized in a
single system. The targeted synergy between these multiple
physical phenomena for Ln3+ materials requires placing the Ln3+
magnetic spins in an extended framework with the appropriate NCS
lattice symmetry.[7]
The design of lanthanide compounds with a NCS crystal structure,
however, constitutes a significant synthetic challenge due to the
intrinsic constraints of controlling both local and extended structures
simultaneously.[8] To overcome this, we combined three (SeO3)2-,
(SO4)2-, and H2O building units to create new NCS chiral polar
lanthanide compounds.[9] In addition to framing the NCS lattice
symmetry, these ligands with different electronic polarizabilities can
impart favorable optical responses, offering possibilities for realizing
unique multifunctional phenomena.[10]
The conventional approach to synthesizing mixed anion compounds
often involves annealing a mixture of reactive oxides and halides at
high temperatures or reacting those reagents in an aqueous solution
of HX (X = F, Cl).[11] These synthetic methods often yield complex
product mixtures, hindering chemical control of targeted materials,
and thus limiting meaningful study and understanding of electron,
spin, orbital, and phonon coupling.
RESEARCH ARTICLE
2
Figure 1. (a-b) Crystal structure of Ln2(SeO3)2(SO4)(H2O)2 consisting of chains of edge-shared LnO7(H2O) square antiprisms, (SeO3)2-
trigonal pyramids, and (SO4)2- tetrahedra. The LnO7(H2O) square antiprism is aligned along the b-axis, resulting in the macroscopic electric
polarization. (c) LnO7(H2O) edge-sharing square antiprisms forming a 1-D zig-zag chain of Ln3+ spins. (d-f) Rietveld refinement of powder
XRD data for Ln2(SeO3)2(SO4)(H2O)2respectively, showing the excellent agreement between the powder XRD and single crystal XRD data.
Ln O
S
Se
H
Ln
O
SSe
H
Ln
O
H
a
b
c
Ln = Sm, Dy, Yb
20 40 60 80
Intensity (a.u.)
2
θ
(°)
Sm
2
(SeO
3
)
2
(SO
4
)(H
2
O)
2
Measurement
Simulation
Difference
Sm
2
(SeO
3
)
2
(SO
4
)(H
2
O)
2
20 40 60 80
Intensity (a.u.)
2
θ
(°)
Yb
2
(SeO
3
)
2
(SO
4
)(H
2
O)
2
Measurement
Simulation
Difference
Yb
2
(SeO
3
)
2
(SO
4
)(H
2
O)
2
20 40 60 80
Measurement
Simulation
Difference
Dy
2
(SeO
3
)
2
(SO
4
)(H
2
O)
2
Intensity (a.u.)
2
θ
(°)
Dy
2
(SeO
3
)
2
(SO
4
)(H
2
O)
2
d
e
f
摘要：

RESEARCHARTICLE1Ln2(SeO3)2(SO4)(H2O)2(Ln=Sm,Dy,Yb):AMixed-LigandPathwaytoNewLanthanide(III)MultifunctionalMaterialsFeaturingNonlinearOpticalandMagneticAnisotropyPropertiesEbubeE.Oyeka,[a]MichałJ.Winiarski,[b]HannaŚwiątek,[b]WyattBalliew,[a]ColinD.McMillen,[a]MingliLiang,[c]MauriceSorollaII,[d]andTha...

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