Structural Modulation of Fluorescent Rhodamine-Based Dysprosium(III) Single-Molecule Magnets

Mei Jiao Liu; Shu Qi Wu; Jia Xin Li; Yi Quan Zhang; Osamu Sato; Hui Zhong Kou

doi:10.1021/acs.inorgchem.9b03105

Structural Modulation of Fluorescent Rhodamine-Based Dysprosium(III) Single-Molecule Magnets

Mei Jiao Liu, Shu Qi Wu, Jia Xin Li, Yi Quan Zhang, Osamu Sato, Hui Zhong Kou

Department of Fundamental Organic Chemistry

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

Abstract

Two rhodamine 6G-based mononuclear dysprosium complexes, [Dy(L^R)(L^A)₂](ClO₄)₃·Et₂O·1.5MeOH·0.5H₂O (1) and [Dy(L^R)(H₂O)₄(MeCN)](ClO₄)₃·2H₂O·MeCN (2) (L^R = salicylaldehyde rhodamine 6G hydrazone, L^A = 2-pyridylcarboxaldehyde benzoyl hydrazone), are synthesized, aiming at improving the magnetic behavior by modulating their coordination environment. Both complexes own one exclusive short Dy-O_phenoxy coordination bond as the predominant bond and exhibit single-molecule magnet behavior under zero dc field with the energy barrier (U_eff/k_B) of 90 K (1) and 320 K (2) and apparent hysteresis at 1.9 K. The ab initio calculations indicate that the short Dy-O_phenoxy bond determines the direction of magnetic anisotropic axis for 1 and 2. The quantum tunneling of magnetization (QTM) between the ground Kramers doublets (KDs) in 1 cannot be neglected, leading to an experimental U_eff/k_B much lower than the calculated energy of the first excited state (318.2 K). For 2, the stronger magnetic anisotropy and negligible QTM between the ground KDs guarantees that the energy barrier is close to the calculated energy of first KDs (320.8 K). On the other hand, the presence of ring-opened xanthene moiety makes complexes 1 and 2 in the solid state emit red light with emission bands of 645 and 658 nm, respectively.

Original language	English
Pages (from-to)	2308-2315
Number of pages	8
Journal	Inorganic chemistry
Volume	59
Issue number	4
DOIs	https://doi.org/10.1021/acs.inorgchem.9b03105
Publication status	Published - Feb 17 2020

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.9b03105

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@article{3dd214fa650f4e378ad1ee7bc6f3d3b2,

title = "Structural Modulation of Fluorescent Rhodamine-Based Dysprosium(III) Single-Molecule Magnets",

abstract = "Two rhodamine 6G-based mononuclear dysprosium complexes, [Dy(LR)(LA)2](ClO4)3·Et2O·1.5MeOH·0.5H2O (1) and [Dy(LR)(H2O)4(MeCN)](ClO4)3·2H2O·MeCN (2) (LR = salicylaldehyde rhodamine 6G hydrazone, LA = 2-pyridylcarboxaldehyde benzoyl hydrazone), are synthesized, aiming at improving the magnetic behavior by modulating their coordination environment. Both complexes own one exclusive short Dy-Ophenoxy coordination bond as the predominant bond and exhibit single-molecule magnet behavior under zero dc field with the energy barrier (Ueff/kB) of 90 K (1) and 320 K (2) and apparent hysteresis at 1.9 K. The ab initio calculations indicate that the short Dy-Ophenoxy bond determines the direction of magnetic anisotropic axis for 1 and 2. The quantum tunneling of magnetization (QTM) between the ground Kramers doublets (KDs) in 1 cannot be neglected, leading to an experimental Ueff/kB much lower than the calculated energy of the first excited state (318.2 K). For 2, the stronger magnetic anisotropy and negligible QTM between the ground KDs guarantees that the energy barrier is close to the calculated energy of first KDs (320.8 K). On the other hand, the presence of ring-opened xanthene moiety makes complexes 1 and 2 in the solid state emit red light with emission bands of 645 and 658 nm, respectively.",

author = "Liu, {Mei Jiao} and Wu, {Shu Qi} and Li, {Jia Xin} and Zhang, {Yi Quan} and Osamu Sato and Kou, {Hui Zhong}",

note = "Funding Information: This work was supported by the National Natural Science Foundation of China (21571113, 21771115, 11774178, and 21973046).",

year = "2020",

month = feb,

day = "17",

doi = "10.1021/acs.inorgchem.9b03105",

language = "English",

volume = "59",

pages = "2308--2315",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "4",

}

TY - JOUR

T1 - Structural Modulation of Fluorescent Rhodamine-Based Dysprosium(III) Single-Molecule Magnets

AU - Liu, Mei Jiao

AU - Wu, Shu Qi

AU - Li, Jia Xin

AU - Zhang, Yi Quan

AU - Sato, Osamu

AU - Kou, Hui Zhong

N1 - Funding Information: This work was supported by the National Natural Science Foundation of China (21571113, 21771115, 11774178, and 21973046).

PY - 2020/2/17

Y1 - 2020/2/17

N2 - Two rhodamine 6G-based mononuclear dysprosium complexes, [Dy(LR)(LA)2](ClO4)3·Et2O·1.5MeOH·0.5H2O (1) and [Dy(LR)(H2O)4(MeCN)](ClO4)3·2H2O·MeCN (2) (LR = salicylaldehyde rhodamine 6G hydrazone, LA = 2-pyridylcarboxaldehyde benzoyl hydrazone), are synthesized, aiming at improving the magnetic behavior by modulating their coordination environment. Both complexes own one exclusive short Dy-Ophenoxy coordination bond as the predominant bond and exhibit single-molecule magnet behavior under zero dc field with the energy barrier (Ueff/kB) of 90 K (1) and 320 K (2) and apparent hysteresis at 1.9 K. The ab initio calculations indicate that the short Dy-Ophenoxy bond determines the direction of magnetic anisotropic axis for 1 and 2. The quantum tunneling of magnetization (QTM) between the ground Kramers doublets (KDs) in 1 cannot be neglected, leading to an experimental Ueff/kB much lower than the calculated energy of the first excited state (318.2 K). For 2, the stronger magnetic anisotropy and negligible QTM between the ground KDs guarantees that the energy barrier is close to the calculated energy of first KDs (320.8 K). On the other hand, the presence of ring-opened xanthene moiety makes complexes 1 and 2 in the solid state emit red light with emission bands of 645 and 658 nm, respectively.

AB - Two rhodamine 6G-based mononuclear dysprosium complexes, [Dy(LR)(LA)2](ClO4)3·Et2O·1.5MeOH·0.5H2O (1) and [Dy(LR)(H2O)4(MeCN)](ClO4)3·2H2O·MeCN (2) (LR = salicylaldehyde rhodamine 6G hydrazone, LA = 2-pyridylcarboxaldehyde benzoyl hydrazone), are synthesized, aiming at improving the magnetic behavior by modulating their coordination environment. Both complexes own one exclusive short Dy-Ophenoxy coordination bond as the predominant bond and exhibit single-molecule magnet behavior under zero dc field with the energy barrier (Ueff/kB) of 90 K (1) and 320 K (2) and apparent hysteresis at 1.9 K. The ab initio calculations indicate that the short Dy-Ophenoxy bond determines the direction of magnetic anisotropic axis for 1 and 2. The quantum tunneling of magnetization (QTM) between the ground Kramers doublets (KDs) in 1 cannot be neglected, leading to an experimental Ueff/kB much lower than the calculated energy of the first excited state (318.2 K). For 2, the stronger magnetic anisotropy and negligible QTM between the ground KDs guarantees that the energy barrier is close to the calculated energy of first KDs (320.8 K). On the other hand, the presence of ring-opened xanthene moiety makes complexes 1 and 2 in the solid state emit red light with emission bands of 645 and 658 nm, respectively.

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U2 - 10.1021/acs.inorgchem.9b03105

DO - 10.1021/acs.inorgchem.9b03105

M3 - Article

C2 - 31984736

AN - SCOPUS:85079563322

SN - 0020-1669

VL - 59

SP - 2308

EP - 2315

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 4

ER -

Structural Modulation of Fluorescent Rhodamine-Based Dysprosium(III) Single-Molecule Magnets

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