The first anion template cubic cyanometallate cage and its 3,5-dimethyltris(pyrazolyl)methane iron(II,III) tricyanide building blocks

Shi, Chu-Chen; Chen, Chi-Shian; Hsu, Sodio C. N.; Yeh, Wen-Yann; Chiang, Michael Y.; Kuo, Ting‐Shen

doi:10.1016/j.inoche.2008.07.022

Cited by 10 publications

(1 citation statement)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, by substituting the labile coordinated solvent molecule with the monodentate imidazole ligand (Im) on the nickel(II) ions, we managed to isolate and characterize in solution and in the solid-state the Cs⊂{[Fe(Tp)(CN) 3 ] 4 [Ni II (Im) 3 ] 4 } cubes. So far, only two other examples of such cubes bearing monodentate ligands have been reported in the literature: a type of procube, {[M(tach)(CN) 3 ] 4 [M′(H 2 O) 3 ] 4 } (M = Co, Fe; M′ = Fe, Co, Ni, tach = cis,cis- 1,3,5-triaminocyclohexane) and the anion-templating BF 4 ⊂{[Fe(Tp*)(CN) 3 ] 4 [Fe(H 2 O) 3 ] 4 }·(BF 4 ) 3 , where the second metal ion is coordinated by solvent water molecules. Additionally, a {Fe II 4 Ni II 4 } cube bearing a bidentate ligand on the Ni(II) metal ion and a CH 3 CN solvent molecule to complete the coordination sphere was also isolated with the formula: {[Fe II (pzTp)(CN) 3 ] 4 [Ni II 4 (phen)(CH 3 CN)]} .…”

Section: Resultsmentioning

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

View full text Add to dashboard Cite

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.

show abstract

Section: Resultsmentioning

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

View full text Add to dashboard Cite

show abstract

Template Synthesis

and¹,

Lindoy²

2011

Anion Coordination Chemistry

View full text Add to dashboard Cite

Stepwise and Self-Assembly Synthesis of Tetranuclear Iron-Thiolate-Diisocyanide Metallocyclophane Complexes

Huang

Cheng

et al. 2016

Journal of the Chinese Chemical Society

Self Cite

View full text Add to dashboard Cite

Treatment of known complex [Cp2Fe2 (μ‐SEt)2(CH3CN)2](BF4 )2 (1(BF4 )2) with 2 equiv of 1,4‐bis(isocyanomethyl)benzene (1,4‐CNCH2C6H4CH2NC; L1 ) or 4,4′‐diisocyanophenyl ether (4,4′‐CNC6H4OC6H4NC; L2 ) result in the formation of two new‐type diisocyanide complexes [Cp2Fe2 (μ‐SEt)2(1,4‐CNCH2C6H4CH2NC)2](BF4 )2 (2a(BF4 )2) or [Cp2Fe2 (μ‐SEt)2(4,4′‐CNC6H4OC6H4NC)2](BF4 )2 (2b(BF4 )2), respectively. The new‐type 24‐membered ring tetranuclear iron–thiolate–aryldiisocyanide metallocyclophane complex [Cp4Fe4 (μ‐SEt)4(μ‐1,4‐CNCH2C6H4CH2NC)2](BF4 )4 (3a(BF4 )4) has been synthesized by using a self‐assembly reaction between equimolar amounts of 1(BF4 )2 and 1,4‐bis(isocyanomethyl)benzene or by a stepwise route involving mixing a 1:1 molar ratio of complexes 1(BF4 )2 and 2a(BF4 )2. A similar approach was used through the application of equal molar ratio of complexes 1(BF4 )2 and 2b(BF4 )2 to give a 30‐membered ring tetranuclear iron–thiolate–aryldiisocyanide metallocyclophane complex [Cp4Fe4 (μ‐SEt)4(4,4′‐CNC6H4OC6H4NC)2][BF4 ]4 (3b(BF4 )4). The spectroscopic and electrochemical properties of four iron–sulfur core complexes were determined.

show abstract

The first anion template cubic cyanometallate cage and its 3,5-dimethyltris(pyrazolyl)methane iron(II,III) tricyanide building blocks

Cited by 10 publications

References 35 publications

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

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

Template Synthesis

Stepwise and Self-Assembly Synthesis of Tetranuclear Iron-Thiolate-Diisocyanide Metallocyclophane Complexes

Contact Info

Product

Resources

About

The first anion template cubic cyanometallate cage and its 3,5-dimethyltris(pyrazolyl)methane iron(II,III) tricyanide building blocks

Cited by 10 publications

References 35 publications

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

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

Template Synthesis

Stepwise and Self-Assembly Synthesis of Tetranuclear Iron-Thiolate-Diisocyanide Metallocyclophane Complexes

Contact Info

Product

Resources

About

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

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