Cyanide-bridged assemblies with tricyanometalates

Shiga, Tohru; Mihara, Nozomi; Nihei, Masayuki

doi:10.1016/j.ccr.2022.214763

Cited by 20 publications

(9 citation statements)

References 152 publications

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“…Another approach to achieve molecular squares was the employment of heteroleptic metalloligands taking advantage of the rich library of the di-, tri-, and tetracyanido 3 d building-blocks, in which the smaller number of coordination sites should favor the formation of low-dimensional/oligonuclear complexes. − Moreover, special attention has to be paid to the position of the peripheral cyanide ligands on the heteroleptic 3 d cyanido-based complexes in order to fulfill the geometrical requirements to direct the assembling process toward the formation of squares.…”

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

confidence: 99%

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%

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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“…External-stimuli-responsive inter-or intramolecular electron transfer can trigger electronic state configuration and magnetic state changes. [55][56][57][58][59][60][61][62][63][64] One electron is exchanged between a donor (D) and acceptor (A), resulting in two valence isomers, namely, neutral DA and ionic D + A À , which can be controlled by modulating the difference in the redox potential of the D/A units. [65][66][67] Zheng et al reported an ME phenomenon in a mixedvalence trinuclear Fe complex, [Fe 3 O(CH 3 COO) 6 (py) 3 ](py) (py = pyridine) (Figure 4), [68] which was investigated as a new MD material.…”

Section: Effect Demonstrated In a Mixed-valence Discrete Coordination...mentioning

confidence: 99%

“…External‐stimuli‐responsive inter‐ or intramolecular electron transfer can trigger electronic state configuration and magnetic state changes [55–64] . One electron is exchanged between a donor (D) and acceptor (A), resulting in two valence isomers, namely, neutral DA and ionic D + A − , which can be controlled by modulating the difference in the redox potential of the D/A units [65–67] …”

Section: Effect In Discrete Coordination Metal Complexesmentioning

confidence: 99%

Coupling Dielectric Functionality with Magnetic Properties in Coordination Metal Complexes

et al. 2023

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Significant research has been conducted on molecular ferroelectric materials, including pure organic and inorganic compounds; however, studies on ferroelectric materials based on coordination metal complexes are scarce. Ferroelectric materials based on coordination metal complexes have tunable structures and designs, with coexistence or synergy between the ferroelectric behavior and magnetic properties. Compared to inorganic compounds, few coordination metal complexes exhibit coupling between the magnetic and dielectric properties. Coordination metal complexes with strong coupling between the magnetic and dielectric properties exhibit dielectric permittivity variations under external magnetic fields. Therefore, they have attracted substantial interest for their potential use in magnetoelectric devices. In this review, we discuss recent advances in coordination metal complexes, that exhibit coupled magnetic functionalities and ferroelectricity or dielectric properties, including single‐molecule magnets, electron delocalization systems, and external stimuli responsive compounds.

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“…Blocked cyanido-complexes [M(L)(CN) x ] − were specifically designed and used to target such low-dimensional complexes. − For instance, researchers from our group prepared the fac -[Fe III (Tp)(CN) 3 ] − (Tp = hydro-tris(pyrazol-1-yl-borate) which has been extensively used since then together with its derivates fac -[Fe III (RTp)(CN) 3 ] − (RTp are tris(pyrazol-1-yl-borate derivatives) . Herein, the choice of blocking ligand, L, is crucial as it affects the metallo-ligand’s electronic properties and topology and thus allows controlling the architecture and properties of the assembled complexes. ,, However, also synthetic conditions may drastically influence the resulting topology.…”

Section: Introductionmentioning

confidence: 99%

Design of Redox-Active Cs⊂{Fe₄Ni₄} Cyanide-Bridged Cage Complexes Bearing Monodentate Ligands: Synthesis, Structure, and Electronic Properties

Glatz

Donnart

Gontard

et al. 2023

Crystal Growth & Design

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In recent years, strong efforts have been devoted to the design and crystallization of molecular models of the cyanidobridged inorganic polymers known as "Prussian Blue Analogues" (PBA). In this work, we more specifically focus on soluble octametallic complexes that represent an elemental unit of the PBA cubic network. The self-assembly of tris-cyanido, the fac-[Fe III (Tp)(CN) 3 ] − (Tp = hydro-tris(pyrazol-1-yl-borate) complex, and Ni(II) salts is shown to lead to {[Fe(Tp)(CN) 3 ] 4 [Ni(S) 3 ] 4 } procubes, where the Ni(II) ions are coordinated to labile solvent molecules (S: DMF or CH 3 CN). 1 H and 133 Cs paramagnetic NMR studies show that (i) the cubic complex is relatively stable during several days in solution, in particular in acetonitrile and (ii) a Cs + ion can be inserted inside the cubic cavity as revealed by the presence of a strongly shifted 133 Cs paramagnetic signal near −800 ppm at 300 K. The resulting Cs⊂{[Fe(Tp)(CN) 3 ] 4 [Ni(S) 3 ] 4 } 5+ procube shows an enhanced stability as shown by time dependent 1 H and 133 Cs paramagnetic NMR spectra collected during several weeks. FT-IR spectra confirm the expected Fe(III) and Ni(II) redox states, with the occurrence of a single characteristic cyanide stretching vibration near 2170 cm −1 . The Fe(III) redox state is also confirmed by cyclic voltammetry experiments in acetonitrile, with the occurrence of four pseudoreversible reduction events that can be assigned to the successive reduction of the Fe III ions in the Cs procube. Although these procubes could not be isolated as single crystals, the substitution of the labile coordinated solvent of the Cs-containing procube by N-donor imidazole monodentate ligands allows the crystallization of the novel Cs⊂{[Fe(Tp)(CN) 3 ] 4 -[Ni II (Im) 3 ] 4 }Cl 3 (Im = 1H imidazole) cubic complex by slow diffusion of ether into a DMF mother solution. The analyses of this cube demonstrate that in solution in ambient condition, Fe(III) centers are gradually reduced to Fe(II). The presence of three chlorides as counterions suggests that the cube can be isolated in the Fe II 2 Fe III 2 Ni II 4 redox state. The presence of at least two Fe(II) ions is actually confirmed by cyclic voltammetry experiment in DMF and FT-IR spectroscopy. An intermediate state Fe II Fe III 3 Ni II 4can be isolated by isolating fresh crystals (ca. 72 h) as demonstrated by FT-IR, cyclic voltammetry, and the magnetic measurements, that also reveal the presence of paramagnetic ferromagnetic interactions between the low-spin Fe III and Ni II ions.

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Cyanide-bridged assemblies with tricyanometalates

Cited by 20 publications

References 152 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

Coupling Dielectric Functionality with Magnetic Properties in Coordination Metal Complexes

Design of Redox-Active Cs⊂{Fe₄Ni₄} Cyanide-Bridged Cage Complexes Bearing Monodentate Ligands: Synthesis, Structure, and Electronic Properties

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Cyanide-bridged assemblies with tricyanometalates

Cited by 20 publications

References 152 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

Coupling Dielectric Functionality with Magnetic Properties in Coordination Metal Complexes

Design of Redox-Active Cs⊂{Fe4Ni4} Cyanide-Bridged Cage Complexes Bearing Monodentate Ligands: Synthesis, Structure, and Electronic Properties

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Design of Redox-Active Cs⊂{Fe₄Ni₄} Cyanide-Bridged Cage Complexes Bearing Monodentate Ligands: Synthesis, Structure, and Electronic Properties