Chiral six-coordinate Dy(iii) and Tb(iii) complexes of an achiral ligand: structure, fluorescence, and magnetism
Two new chiral six-coordinate lanthanide complexes (1 for Dy and 2 for Tb) have been synthesized using the achiral flexible ligand H L (2,2'-[1,2-ethanediylbis[(methylimino)methylene]]bis[4,5-dimethylphenol]). Both complexes crystallize in the chiral P1 group space, and the enantiomers [Zn(L)Cl...
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| Published in | Dalton transactions : an international journal of inorganic chemistry Vol. 46; no. 38; pp. 13035 - 13042 |
|---|---|
| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
England
14.10.2017
|
| Online Access | Get full text |
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| Abstract | Two new chiral six-coordinate lanthanide complexes (1 for Dy and 2 for Tb) have been synthesized using the achiral flexible ligand H
L (2,2'-[1,2-ethanediylbis[(methylimino)methylene]]bis[4,5-dimethylphenol]). Both complexes crystallize in the chiral P1 group space, and the enantiomers [Zn(L)Cl]
Dy·MeOH·0.5H
O (Λ-1), [Zn(L)Cl]
Dy·1.5H
O (Δ-1), [Zn(L)Cl]
Tb·1.5H
O (Λ-2) and [Zn(L)Cl]
Tb·H
O (Δ-2) are isolated in the reaction. Three [Zn(L)Cl]
anions coordinate to the central lanthanide ion using two phenoxo oxygen atoms of L
, and the lanthanide ion has the coordination geometry of D
. Complex 1 exhibits a field-induced slow magnetization relaxation, which is typical of a single-ion magnet (SIM). Ab initio calculations on complex 1 and studies on magneto-structural correlationship of six-coordinate Dy(iii) SIMs indicate that the small energy barrier of complex 1 might be related to the absence of a unique anisotropic axis for the regular octahedral coordination configuration of Dy(iii) and the high quantum tunneling gap between the ground states (m
= ±15/2). Complex 2 displays green photofluorescence and triboluminescence. |
|---|---|
| AbstractList | Two new chiral six-coordinate lanthanide complexes (
1
for Dy and
2
for Tb) have been synthesized using the achiral flexible ligand H
2
L (2,2′-[1,2-ethanediylbis[(methylimino)methylene]]bis[4,5-dimethylphenol]). Both complexes crystallize in the chiral
P
1 group space, and the enantiomers [Zn(L)Cl]
3
Dy·MeOH·0.5H
2
O (
Λ-1
), [Zn(L)Cl]
3
Dy·1.5H
2
O (
Δ-1
), [Zn(L)Cl]
3
Tb·1.5H
2
O (
Λ-2
) and [Zn(L)Cl]
3
Tb·H
2
O (
Δ-2
) are isolated in the reaction. Three [Zn(L)Cl]
−
anions coordinate to the central lanthanide ion using two phenoxo oxygen atoms of L
2−
, and the lanthanide ion has the coordination geometry of
D
3
. Complex
1
exhibits a field-induced slow magnetization relaxation, which is typical of a single-ion magnet (SIM).
Ab initio
calculations on complex
1
and studies on magneto-structural correlationship of six-coordinate Dy(
iii
) SIMs indicate that the small energy barrier of complex
1
might be related to the absence of a unique anisotropic axis for the regular octahedral coordination configuration of Dy(
iii
) and the high quantum tunneling gap between the ground states (
m
J
= ±15/2). Complex
2
displays green photofluorescence and triboluminescence. Two new chiral six-coordinate lanthanide complexes (1 for Dy and 2 for Tb) have been synthesized using the achiral flexible ligand H2L (2,2'-[1,2-ethanediylbis[(methylimino)methylene]]bis[4,5-dimethylphenol]). Both complexes crystallize in the chiral P1 group space, and the enantiomers [Zn(L)Cl]3Dy·MeOH·0.5H2O (Λ-1), [Zn(L)Cl]3Dy·1.5H2O (Δ-1), [Zn(L)Cl]3Tb·1.5H2O (Λ-2) and [Zn(L)Cl]3Tb·H2O (Δ-2) are isolated in the reaction. Three [Zn(L)Cl]- anions coordinate to the central lanthanide ion using two phenoxo oxygen atoms of L2-, and the lanthanide ion has the coordination geometry of D3. Complex 1 exhibits a field-induced slow magnetization relaxation, which is typical of a single-ion magnet (SIM). Ab initio calculations on complex 1 and studies on magneto-structural correlationship of six-coordinate Dy(iii) SIMs indicate that the small energy barrier of complex 1 might be related to the absence of a unique anisotropic axis for the regular octahedral coordination configuration of Dy(iii) and the high quantum tunneling gap between the ground states (mJ = ±15/2). Complex 2 displays green photofluorescence and triboluminescence. Two new chiral six-coordinate lanthanide complexes (1 for Dy and 2 for Tb) have been synthesized using the achiral flexible ligand H L (2,2'-[1,2-ethanediylbis[(methylimino)methylene]]bis[4,5-dimethylphenol]). Both complexes crystallize in the chiral P1 group space, and the enantiomers [Zn(L)Cl] Dy·MeOH·0.5H O (Λ-1), [Zn(L)Cl] Dy·1.5H O (Δ-1), [Zn(L)Cl] Tb·1.5H O (Λ-2) and [Zn(L)Cl] Tb·H O (Δ-2) are isolated in the reaction. Three [Zn(L)Cl] anions coordinate to the central lanthanide ion using two phenoxo oxygen atoms of L , and the lanthanide ion has the coordination geometry of D . Complex 1 exhibits a field-induced slow magnetization relaxation, which is typical of a single-ion magnet (SIM). Ab initio calculations on complex 1 and studies on magneto-structural correlationship of six-coordinate Dy(iii) SIMs indicate that the small energy barrier of complex 1 might be related to the absence of a unique anisotropic axis for the regular octahedral coordination configuration of Dy(iii) and the high quantum tunneling gap between the ground states (m = ±15/2). Complex 2 displays green photofluorescence and triboluminescence. |
| Author | Kou, Hui-Zhong Liu, Mei-Jiao Sun, Hao-Ling Zhang, Yi-Quan Yuan, Juan Liu, Cai-Ming |
| Author_xml | – sequence: 1 givenname: Mei-Jiao surname: Liu fullname: Liu, Mei-Jiao email: kouhz@mail.tsinghua.edu.cn organization: Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China. kouhz@mail.tsinghua.edu.cn – sequence: 2 givenname: Juan surname: Yuan fullname: Yuan, Juan – sequence: 3 givenname: Yi-Quan surname: Zhang fullname: Zhang, Yi-Quan – sequence: 4 givenname: Hao-Ling surname: Sun fullname: Sun, Hao-Ling – sequence: 5 givenname: Cai-Ming surname: Liu fullname: Liu, Cai-Ming – sequence: 6 givenname: Hui-Zhong surname: Kou fullname: Kou, Hui-Zhong |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/28937175$$D View this record in MEDLINE/PubMed |
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| Snippet | Two new chiral six-coordinate lanthanide complexes (1 for Dy and 2 for Tb) have been synthesized using the achiral flexible ligand H
L... Two new chiral six-coordinate lanthanide complexes ( 1 for Dy and 2 for Tb) have been synthesized using the achiral flexible ligand H 2 L... Two new chiral six-coordinate lanthanide complexes (1 for Dy and 2 for Tb) have been synthesized using the achiral flexible ligand H2L... |
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| Title | Chiral six-coordinate Dy(iii) and Tb(iii) complexes of an achiral ligand: structure, fluorescence, and magnetism |
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