Single‐Molecule Magnet Behavior in Two Tetranuclear Cyanide‐bridged FeIII2NiII2 Compounds

Liu, Xue-Ru; Jiao, Cheng‐Qi; Meng, Yin‐Shan; Zhu, Hai‐Lang; Jiang, Wen-Jing; Wen, Wen; Zhao, Liang; Liu, Tao

doi:10.1002/zaac.201800401

Cited by 2 publications

(5 citation statements)

References 32 publications

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“…Consequently, the d - d / d ′ squares became a very fruitful research area devoted to the magnetic behavior of the tetranuclear PBAs. Among the cyanido building-blocks, the dicyano-[Fe II/III (AA) 2 (CN) 2 ] n+ (AA = didentate ligand; n = 0 and 1) − and tricyano- fac -[M(CN) 3 {RB(R′(pz) 3 }] (R = H, methyl, 2-methyl propyl, pyrazol; R′ = H, methyl) derivatives − proved to be suitable to synthesize molecular squares in their reactions with 3 d metal ions whose coordination sphere is partially blocked with didentate AA ligands, such as bipy, 4,4′-dimethyl 2,2′-bipyridine (4,4′-Me 2 bipy), and 1,10-phenantroline (phen) or a tridentate one coordinated to the M III cation in a fac stereochemistry.…”

Section: Strategies To Assemble Cyanido-bridged D-d/d-d′ Heterometall...mentioning

confidence: 99%

“…The cyanido-based fac -[Fe III (CN) 3 {RB(R 1–3 (pz) 3 }] − complexes, bearing three coordination sites blocked by the pyrazolylborate type ligand and three terminal cyanide groups in a fac arrangement, were extensively used to assemble molecular squares (R = H, 2-methylpropyl, pyrazol; R 1,2,3 = H, methyl; Scheme ). Therefore, the resulting d - d / d ′ square-like tetranuclear compounds became a rich area of investigation of reversible thermal-/light-/X-ray induced magnetism, ,− spin crossover, − as well as slow relaxation of the magnetization and SMM properties. − …”

Section: Strategies To Assemble Cyanido-bridged D-d/d-d′ Heterometall...mentioning

confidence: 99%

“…The nanomagnets with discrete structure and a square-like topology represent another appealing family of low-dimensional PBAs in which the quantum effects, like slow relaxation of the magnetization or quantum tunneling, become active and, therefore, open new windows concerning the molecular design of new types of memory devices or in quantum computing. The inclusion of a highly anisotropic 3 d metal into a square-like molecule led to interesting examples of cyanido-bridged SIMs and SMMs. − ,− …”

Section: Strategies To Assemble Cyanido-bridged D-d/d-d′ Heterometall...mentioning

confidence: 99%

“…The obtained Fe III and Ni II -containing ferromagnetic squares exhibited SMM properties. Liu et al . concluded that the additional pyrazolyl ring on the [{B(pz) 4 }Fe III (CN) 3 ] − unit compared to [{HB(pz) 3 }Fe(CN) 3 ] − ion results in the enhancement of the π–π supramolecular interactions between neighboring squares with the effect of suppressing the SMM properties by decreasing the energy barrier from 47.9 cm –1 for the HB(pz) 3 – derivative to 8.76 cm –1 for the B(pz) 4 – containing analogue.…”

Section: Strategies To Assemble Cyanido-bridged D-d/d-d′ Heterometall...mentioning

confidence: 99%

“…This compound showed frequency-dependence of the in-phase (χ′) and out-of-phase (χ″) magnetic susceptibilities, with τ 0 = 1.4 × 10 –7 s and an effective energy barrier of 10.9 cm –1 under H dc = 2200 Oe . Other types of cyanido-based metalloligands, such as [{(B(pz) 4 }Fe III (CN) 3 ] − , [{HB(pz) 3 }Fe(CN) 3 ] − , or [{ i -BuB(pz) 3 }Fe(CN) 3 ] − entities [ i -BuB(pz) 3 – = 2-methylpropyltris(pyrazolyl)borate], afforded square-like molecules in their combination with Ni II ions whose coordination sphere is partially blocked with didentate ligands, such as 2,2′-dipyridyl amine (dpa), 4-chlorine-2,2′-bipyridine (4-Clbpy), 4,4′-dichloro-2,2′-bipyridine (4,4′-Cl 2 bpy), or π-conjugated sulfur-rich chelating ligands like 4,5-[10,40]dithiino[20,30-b]quinoxaline-2-bis(2-pyridyl)methylene-1,3-dithiole and 4,5-bis(methylthio)-2-bis(2-pyridyl)methylene-1,3-dithiole ligands . The obtained Fe III and Ni II -containing ferromagnetic squares exhibited SMM properties.…”

Section: Strategies To Assemble Cyanido-bridged D-d/d-d′ Heterometall...mentioning

confidence: 99%

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Cyanido-Bridged Heterobimetallic Molecular Squares: Low-Dimensional Models of Prussian Blue Analogues and Beyond

Alexandru

Visinescu

Cano

et al. 2023

Crystal Growth & Design

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The cyanido-bridged square-like molecules with d/f metal ions occupying the corners of the square are considered molecular models of the Prussian Blue Analogues (PBAs) because they reproduce one face of their 3D face-centered cubic structure, being called low-dimensional PBAs. Such highly regular complexes provide unique insights into the short-range magnetic exchange interaction between the metal ions of PBAs and exhibit magnetic properties which are not found for PBAs. This review focuses on the preparative routes and magneto-structural characterization of d-d(d′)/d-f tetranuclears with a square-like topology generating rich families of molecular switches and nanomagnets. Relevant examples that provided a better comprehension of the magnetic behavior of PBAs, including subtle chemical factors that interfere in the photo- and thermally induced electron transfer are reviewed herein. A special attention is paid to the design of d-f cyanido-bridged squares, less numerous compared to the d-d/d′ ones, that proved to be suitable model compounds for the theoretical treatment of the magnetic exchange interaction between d and f spin carriers across the cyanide ligand. The square-shaped PBAs represent a very active area of research that is enriched yearly with new examples with potential for the development of molecular-scaled electronic devices.

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Section: Strategies To Assemble Cyanido-bridged D-d/d-d′ Heterometall...mentioning

confidence: 99%

Section: Strategies To Assemble Cyanido-bridged D-d/d-d′ Heterometall...mentioning

confidence: 99%

Section: Strategies To Assemble Cyanido-bridged D-d/d-d′ Heterometall...mentioning

confidence: 99%

Section: Strategies To Assemble Cyanido-bridged D-d/d-d′ Heterometall...mentioning

confidence: 99%

Section: Strategies To Assemble Cyanido-bridged D-d/d-d′ Heterometall...mentioning

confidence: 99%

See 3 more Smart Citations

Cyanido-Bridged Heterobimetallic Molecular Squares: Low-Dimensional Models of Prussian Blue Analogues and Beyond

Alexandru

Visinescu

Cano

et al. 2023

Crystal Growth & Design

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Structural Modulation of Coordination Polymers by Heterometallic Approach

Zhu

Shi

et al. 2019

Zeitschrift anorg allge chemie

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A series of heterometallic Ni II /Co II coordination polymers with 2D networks were synthesized by tetrazole-1-acetate ligands and structurally characterized. With increasing concentration of cobalt(II), 1062another different connectivity patterns have been observed. The influence of cobalt(II) is not only on the crystallization, but also on the variation of magnetic properties. Scheme 1. Coordination modes of tetrazole-1-acetate ligand. Synthesis ofCompound 4: The ratio of Ni(OAc) 2 ·4H 2 O/CoCl 2 ·6H 2 O was used: 0.49 mmol/ 0.21 mmol. FT-IR (KBr): ν = 3476, 3131, 3002, cm -1 . ICP-AES: for the ratio of Ni : Co = 0.70:0.30. Synthesis of Compound 5: The ratio of Ni(OAc) 2 ·4H 2 O/CoCl 2 ·6H 2 O was used: 0.42 mmol/ 0.28 mmol. cm -1 . ICP-AES for the ratio of Ni : Co = 0.62:0.38. Synthesis of Compound 6: The ratio of Ni(OAc) 2 ·4H 2 O/CoCl 2 ·6H 2 O was used: 0.35 mmol/0.35 mmol. cm -1 . ICP-AES for the ratio of Ni : Co = 0.52:0.48. Synthesis of Compound 7: The ratio of Ni(OAc) 2 ·4H 2 O/CoCl 2 ·6H 2 O was used: 0.28 mmol/0.42 mmol. FT-IR (KBr): ν = 3458, 3137, 3004, , 580 cm -1 . ICP-AES for the ratio of Ni : Co = 0.44:0.56. Supporting Information (see footnote on the first page of this article): XRPD patterns of complexes with different ratio of Ni:Co and additional magnetic data for complexes 1-7.

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Single‐Molecule Magnet Behavior in Two Tetranuclear Cyanide‐bridged Fe^III₂Ni^II₂ Compounds

Cited by 2 publications

References 32 publications

Cyanido-Bridged Heterobimetallic Molecular Squares: Low-Dimensional Models of Prussian Blue Analogues and Beyond

Cyanido-Bridged Heterobimetallic Molecular Squares: Low-Dimensional Models of Prussian Blue Analogues and Beyond

Structural Modulation of Coordination Polymers by Heterometallic Approach

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