Related Experiment Video
Updated: Aug 5, 2026
07:24
Hyperspectral Imaging as a Tool to Study Optical Anisotropy in Lanthanide-Based Molecular Single Crystals
Published on: April 14, 2020
Chiral 3d-4f Clusters with NIR-III Magneto-Optical Activity Driven by Lanthanide f-f Transition
Jia-Nan Chen1, Fu-Li Sun1, Xing Wang1
1State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen361005, China.
Journal of the American Chemical Society
|July 30, 2026
Summary
Chiral molecular clusters show strong magneto-optical effects in the near-infrared III region, driven by lanthanide f-f transitions. This discovery opens new avenues for advanced optical materials and applications.
Area of Science:
- Materials Science
- Magneto-optics
- Chiroptical Spectroscopy
Background:
- Chiral molecular materials with near-infrared III (NIR-III) magneto-optical responses are crucial for photonics and biomedicine.
- Molecular magneto-optical phenomena in the NIR-III region (1600-2500 nm) are underexplored.
- Lanthanide (Ln) f-f transitions are key to optical properties but their NIR-III magneto-optical activity is not well understood.
Purpose of the Study:
- To synthesize and investigate chiral 3d-4f molecular clusters for NIR-III magneto-optical applications.
- To explore the chiroptical and magneto-optical properties of R/S-Ln3Mn4 and R/S-Ln12Mn12 clusters (Ln = HoIII, TbIII, YIII).
- To identify the origin of NIR-III magneto-optical activity in these molecular systems.
Main Methods:
- Synthesis of six pairs of chiral 3d-4f molecular clusters: R/S-Ln3Mn4 and R/S-Ln12Mn12.
- Systematic investigation of chiroptical and magneto-optical properties using Circular Dichroism (CD) and Magnetic Circular Dichroism (MCD) spectroscopy in the NIR-III region.
- Analysis of structural effects (coordination geometry) and magnetic interactions on magneto-optical responses.
Main Results:
- R/S-Ho3Mn4 and R/S-Ho12Mn12 clusters exhibit significant CD and MCD responses in the NIR-III region due to HoIII f-f transitions.
- R/S-Tb3Mn4 and R/S-Tb12Mn12 clusters show strong MCD but no resolved CD signals in the NIR-III region.
- The R/S-Ln12Mn12 series demonstrates enhanced NIR-III MCD responses and larger gMCD values compared to R/S-Ln3Mn4 analogues, attributed to altered coordination geometry and cooperative magnetic interactions.
Conclusions:
- Long-wavelength lanthanide f-f transitions are confirmed as the origin of NIR-III chiroptical and magneto-optical activity in chiral molecular materials.
- Chiral 3d-4f clusters serve as effective platforms for tuning magneto-optical properties in the NIR-III window.
- This study provides the first molecular examples of f-f-transition-driven NIR-III chiroptical and magneto-optical activity, paving the way for novel optical material design.
Related Concept Videos
02:30Chirality at Nitrogen, Phosphorus, and Sulfur
Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
01:16Other Nuclides: 31P, 19F, 15N NMR
Many organic, inorganic, and biological molecules contain spin-half nuclei such as nitrogen-15, fluorine-19, and phosphorus-31. As a result, NMR studies of these nuclei have found extensive applications in chemical and biological research.
While fluorine-19 and phosphorous-31 have high natural abundances (100%) and positive gyromagnetic ratios, nitrogen-15 has a low natural abundance and a negative gyromagnetic ratio. However, nitrogen-15 is still preferred over nitrogen-14 (which has a high...
While fluorine-19 and phosphorous-31 have high natural abundances (100%) and positive gyromagnetic ratios, nitrogen-15 has a low natural abundance and a negative gyromagnetic ratio. However, nitrogen-15 is still preferred over nitrogen-14 (which has a high...
02:42Valence Bond Theory
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
02:52Stereoisomerism
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
01:07Radicals: Electronic Structure and Geometry
This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
03:02Colors and Magnetism
Color in Coordination Complexes
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 eye.
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 eye.