Rare‐Earth Metal Tetrathiafulvalene Carboxylate Frameworks as Redox‐Switchable Single‐Molecule Magnets

Su, Jian; Yuan, Shuai; Li, Jing; Wang, Hai-Ying; Ge, Jing‐Yuan; Drake, Hannah F.; Leong, Chanel F.; Yu, Fei; D’Alessandro, Deanna M.; Kurmoo, Mohamedally; Zuo, Jing‐Lin

doi:10.1002/chem.202004883

Cited by 26 publications

(18 citation statements)

References 53 publications

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“…The thermal stability was investigated. The TGA data for Ln-m-TTFTB showed that the frameworks have good thermal stability up to 450 • C (Figure S5) in the N 2 atmosphere, which is comparable to the Ln-TTFTB series (nearly 500 • C) [28,34].…”

Section: Crystal Structuresmentioning

confidence: 79%

“…Since then, the self-assembly of H 4 TTFTB with diverse metal ions including Cd 2+ , Mn 2+ , Co 2+ , Ba 2+ , Fe 2+/3+ , Mg 2+ , In 3+ , and Zr 4+ has been successfully realized [6,[19][20][21][22][23][24][25][26]. _ENREF_15 In addition, the combination of H 4 TTFTB and lanthanide (Ln) ions has resulted in diverse two dimensional or three-dimensional MOFs [27][28][29][30]. For example, in 2019, Dincă et al reported three polymorphic MOFs containing La 3+ and TTFTB.…”

Section: Introductionmentioning

confidence: 99%

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Redox-Active Metal-Organic Frameworks with Three-Dimensional Lattice Containing the m-Tetrathiafulvalene-Tetrabenzoate

et al. 2022

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Metal−organic frameworks (MOFs) constructed by tetrathiafulvalene-tetrabenzoate (H4TTFTB) have been widely studied in porous materials, while the studies of other TTFTB derivatives are rare. Herein, the meta derivative of the frequently used p-H4TTFTB ligand, m-H4TTFTB, and lanthanide (Ln) metal ions (Tb3+, Er3+, and Gd3+) were assembled into three novel MOFs. Compared with the reported porous Ln-TTFTB, the resulted three-dimensional frameworks, Ln-m-TTFTB ([Ln2(m-TTFTB)(m-H2TTFTB)0.5(HCOO)(DMF)]·2DMF·3H2O), possess a more dense stacking which leads to scarce porosity. The solid-state cyclic voltammetry studies revealed that these MOFs show similar redox activity with two reversible one-electron processes at 0.21 and 0.48 V (vs. Fc/Fc+). The results of magnetic properties suggested Dy-m-TTFTB and Er-m-TTFTB exhibit slow relaxation of the magnetization. Porosity was not found in these materials, which is probably due to the meta-configuration of the m-TTFTB ligand that seems to hinder the formation of pores. However, the m-TTFTB ligand has shown to be promising to construct redox-active or electrically conductive MOFs in future work.

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Section: Crystal Structuresmentioning

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Redox-Active Metal-Organic Frameworks with Three-Dimensional Lattice Containing the m-Tetrathiafulvalene-Tetrabenzoate

et al. 2022

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“…Moreover, the high coordination number and flexible coordination geometry of Dy(III) ions can produce various interesting frameworks. Up to now, multifarious Dy-CPs with slow magnetic relaxation behaviors have been developed ( Wu et al, 2020 ; Song et al, 2021 ; Su et al, 2021 ). Nevertheless, the inherent magnetisms of Dy(III) ions are very sensitive to various factors such as coordination geometry, magnetic interactions, etc., making the performance of Dy(III)-based SMMs difficult to predict ( Pinkowicz et al, 2015 ; Zhang et al, 2015 ; Ge et al, 2020 ).…”

Section: Introductionmentioning

confidence: 99%

Two-dimensional dysprosium(III) coordination polymer: Structure, single-molecule magnetic behavior, proton conduction, and luminescence

Chen

et al. 2022

Front. Chem.

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A new dysprosium (III) coordination polymer [Dy(Hm-dobdc) (H2O)2]·H2O (Dy-CP), was hydrothermal synthesized based on 4,6-dioxido-1,3-benzenedicarboxylate (H4m-dobdc) ligand containing carboxyl and phenolic hydroxyl groups. The Dy(III) center adopts an octa-coordinated [DyO8] geometry, which can be described as a twisted square antiprism (D4d symmetry). Neighboring Dy(III) ions are interconnected by deprotonated Hm-dobdc3− ligand to form the two-dimensional infinite layers, which are further linked to generate three-dimensional structure through abundant hydrogen bonds mediated primarily by coordinated and lattice H2O molecules. Magnetic studies demonstrates that Dy-CP shows the field-induced slow relaxation of magnetization and the energy barrier Ueff/kB and relaxation time τ0 are 35.3 K and 1.31 × 10–6 s, respectively. Following the vehicular mechanism, Dy-CP displays proton conductivity with σ equal to 7.77 × 10–8 S cm−1 at 353 K and 30%RH. Moreover, luminescence spectra reveal that H4m-dobdc can sensitize characteristic luminescence of Dy(III) ion. Herein, good magnetism, proton conduction, and luminescence are simultaneously achieved, and thus, Dy-CP is a potential multifunctional coordination polymer material.

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“…Here, an HGET-induced magnetic phase change was demonstrated in a porous antiferromagnetic layered MOF, [{Ru 2 (2,6-F 2 PhCO 2 ) 4 } 2 (BTDA-TCNQ)] (1; 2,6-F 2 PhCO 2 À = 2,6-difluorobenzoate; BTDA-TCNQ = bis[1,2,5]dithiazolotetracyanoquinodimethane), using iodine (I 2 ) as a redoxactive guest (Schemes 1a, b), which has been reported as an electron acceptor (3 I 2 + 2 e À * * 2 I 3 À ), in some redox-active MOFs [32][33][34][35][36][37][38] and Hofmann-type MOFs. [39,40]…”

Section: Introductionmentioning

confidence: 99%

A Host–Guest Electron Transfer Mechanism for Magnetic and Electronic Modifications in a Redox‐Active Metal–Organic Framework

et al. 2022

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Host-guest electron transfer (HGET) in molecular framework systems is a critical trigger for drastic functional changes in both host framework and guest. A reversible magnetic phase transition was achieved via HGET in a layered framework, [{Ru 2 (2,6-F 2 PhCO 2 ) 4 } 2 (BTDA-TCNQ)] (1), where 2,6-F 2 PhCO 2 À and BTDA-TCNQ represent 2,6-difluorobenzoate and bis[1,2,5]dithiazolotetracyanoquinodimethane, respectively. The guest-free 1 with an antiferromagnetic ground state transformed into a paramagnet, [{Ru 2 (2,6-F 2 PhCO 2 ) 4 } 2 (BTDA-TCNQ)]I 3 (1-I 3 ), by adsorbing iodine (I 2 ). The local charge distribution of [{Ru 2 II,III } + -(BTDA-TCNQ) *À -{Ru 2 II,II }] in 1 was reversibly modified to [{Ru 2 II,III } + -(BTDA-TCNQ) 0 -{Ru 2 II,II }](I 3 À ) in 1-I 3 through HGET. Theoretical calculations of 1-I 3 indicated a partial charge delocalization as [{Ru 2 } (1À δ) + -(BTDA-TCNQ) 0 -{Ru 2 } δ + ](I 3 À ) with δ � 0.2, aided by weak ferromagnetic coupling. 1-I 3 exhibited a hundredfold enhancement in electrical conductivity compared to that of 1.

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Rare‐Earth Metal Tetrathiafulvalene Carboxylate Frameworks as Redox‐Switchable Single‐Molecule Magnets

Cited by 26 publications

References 53 publications

Redox-Active Metal-Organic Frameworks with Three-Dimensional Lattice Containing the m-Tetrathiafulvalene-Tetrabenzoate

Redox-Active Metal-Organic Frameworks with Three-Dimensional Lattice Containing the m-Tetrathiafulvalene-Tetrabenzoate

Two-dimensional dysprosium(III) coordination polymer: Structure, single-molecule magnetic behavior, proton conduction, and luminescence

A Host–Guest Electron Transfer Mechanism for Magnetic and Electronic Modifications in a Redox‐Active Metal–Organic Framework

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