The new decanuclear copper(II) cluster [Cu5(β-alaha)4Cl2]2·2HCl·15H2O, its structure, spectroscopy and magnetism

Legendziewicz, J.; Puchalska, M.; Ciunik, Zbigniew; Wojciechowski, W.

doi:10.1016/j.poly.2006.11.002

Cited by 17 publications

(9 citation statements)

References 31 publications

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“…The anion change resulted in trimerization of the metallacrown moiety, which is at least partly a consequence of the requirement for charge balance (three cations with charge +2 require two anions with charge –3 for neutral compound formation). To the best of our knowledge, this is the first example of such metallacrown oligomerization, though several “dimers” of planar polynuclear metallacrown cations have previously been reported 5h,10,12. In compound 1 , Cr(C 2 O 4 ) 3 3– does not provide a link between pentanuclear moieties, but one oxalate group in each Cr(C 2 O 4 ) 3 3– anion acts as a bridge between Cr III and two Cu II of a single Cu 5 unit.…”

Section: Resultsmentioning

confidence: 73%

A Triple‐Decker Heptadecanuclear (Cu^II)₁₅(Cr^III)₂ Complex Assembled from Pentanuclear Metallacrowns

et al. 2010

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Reaction of the pentanuclear CuII metallacrown [Cu5(ahpha)4](ClO4)·4H2O (ahpha2– is the dianion of 3‐amino‐3‐(hydroximino)propanehydroxamic acid), with Cr(C2O4)33– led to the formation of a heptadecanuclear complex {[Cu5(ahpha)4]3[Cr(C2O4)3]2·4H2O}·8H2O·1/3(DMF) (1·8H2O·1/3(DMF)). This compound contains three stacked Cu5(ahpha)42+ building blocks, linked by axial bonds between Cu2+ ions of one Cu5 metallacrown and hydroxamate oxygen atoms of the neighboring Cu5 unit. Two Cr(C2O4)33– anions are bonded to the two lateral Cu5(ahpha)42+ cations through axial Cu–O(oxalate) bonds. The formation of 1 may be considered the first example of metallacrown trimerization caused by anion metathesis. The compound contains 10 × 13 Å voids (about 25 % of crystal volume), filled with solvate water molecules. The magnetic properties (χMT vs. T) could be fitted as the superposition of the magnetism of 3χMT(CuII5) and 2χMT(CrIII). Exchange interactions within the CuII5 units were fit in the framework of a model based on the Hamiltonian H(CuII5) = –2J1(S1.S5 + S2.S5 + S3.S5 + S4.S5) –2J2(S1.S2 + S2.S3 + S3.S4 + S4.S1), where S5 represents the central Cu2+ ions' spins and the other spin operators correspond to the peripheral Cu2+ ions. With other possible interactions taken into account using a molecular field approach, the best fit correspondedto J1 = –153(5) cm–1, J2 = –71(2) cm–1 and zJ′ = –0.058(4) cm–1.

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Section: Resultsmentioning

confidence: 73%

A Triple‐Decker Heptadecanuclear (Cu^II)₁₅(Cr^III)₂ Complex Assembled from Pentanuclear Metallacrowns

et al. 2010

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“…In the case of monocation salts of anionic metallacrowns {such as NMe 4 + , NEt 4 + , [Na(15‐crown‐5)] + , K + } the metallacrowns are non‐oligomerized , , , . Complexes with cationic metallacrowns and monoanions [NO 3 – , ClO 4 – , OAc – , Cu(OAc) 3 – , Cl – , NO 3 – , HSO 4 – ] generate 1D chains formed by metallacrown units connected through long Cu–O contacts (three compounds), , or non‐oligomerized metallacrowns (nine compounds, including complexes 1 and 2 , vide infra) , , . The presence of counter‐anions or counter‐cations with charges of –2 or +2 {phthalate dianions, SO 4 2– , [Cu(en) 2 ] 2+ } has led to the dimerization of metallacrown units (observed in six complexes),, , , while only one complex containing a counter‐anion of –3 charge, {[Cr(C 2 O 4 )] 3 3– }, has been assembled – with trimerized metallacrown units …”

Section: Resultsmentioning

confidence: 99%

“…In the case of monocation salts of anionic metalla- [52,56,65] or non-oligomerized metallacrowns (nine compounds, including complexes 1 and 2, vide infra). [57,66,67] The presence of counter-anions or counter-cations with charges of -2 or +2 {phthalate dianions, SO 4…”

Section: Mass Spectrometry Studiesmentioning

confidence: 99%

Supramolecular Maleate Adducts of Copper(II) 12‐Metallacrown‐4: Magnetism, EPR, and Alcohol Sorption Properties

et al. 2017

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With maleate, [Cu5(ahpha)4]2+ gives two complexes, [Cu5(ahpha)4(DMF)2](MalH)2·2DMF (1) and [Cu5(ahpha)4(MalH)2] (2) (ahpha2– is 3‐amino‐3‐hydroximinopropane hydroxamate; MalH2 is maleic acid). Both 1 and 2 contain non‐oligomerized [Cu5(ahpha)4]2+ metallacrown blocks; in 1, two MalH– are bound to [Cu5(ahpha)4]2+ only via H‐bonds, while in 2, they coordinate to Cu2+. The X‐band EPR of 1 was observed at 20 K, 100 K, and 295 K. The EPR at 20 K was of an S = 1/2 ground state, while at room temperature anisotropic |ΔMs| = 1 and |ΔMs| = 2 resonances around 3200 G (g ≈ 2.19) and 1600 G (g ≈ 4.25) were observed for the Cu5 system, due to partial occupation of an S = 3/2 state. The room temperature EPR of 1 was simulated as the weighted sum of the spectra of its various S = 1/2, 3/2, and 5/2 states. Its magnetic behavior was fitted with a χMT vs. T model using a spin Hamiltonian accounting for central–peripheral (J1), peripheral–peripheral (J2) Cu2+–Cu2+ and intercrown (zJ′) spin interactions, yielding J1 = –156(4) cm–1, J2 = –63(1) cm–1, and zJ′ = –4.5(3) cm–1. For sorption of methanol and ethanol vapors at 293 K by a desolvated polycrystalline sample of 1, the shape of the adsorption and desorption isotherms indicated a “gates opening” phenomenon.

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“…As regards the dimension of the cavity of the Ni(II) 12-MC-4, the only reported value is that of the 12-MC-4 of Ni(II) and salicylhydroxamic acid (cavity radius = 0.59 Å), 1 while the cavity radius in the structure of [Cu 5 (LH −1 ) 4 ]Cl 2 of β-AlaHA is 0.56 Å. 39,40 In that structure the Ni(II) ion is fivecoordinated and therefore its ionic radius (0.63 Å) almost matches that of the cavity. Here, in solution, we expect a fourcoordinated square planar Ni(II) which has a radius of only 0.49 Å.…”

Section: Metallacrown Formationmentioning

confidence: 99%

Stoichiometric diversity of Ni(ii) metallacrowns with β-alaninehydroxamic acid in aqueous solution

et al. 2013

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The complex-formation equilibria of the system Ni(II)/β-alaninehydroxamic acid (β-AlaHA, LH) have been studied in solution by using potentiometry, calorimetry, ESI mass spectrometry and UV-Visible spectrophotometry. A series of mononuclear and polynuclear species have been identified at different pH and for different Ni(II)/ligand ratios. Among the polymetallic species, we have identified the 12-metallacrown-4 (12-MC-4) species [Ni5(LH(-1))4](2+), which is analogous to the previously characterized [Cu5(LH(-1))4](2+) 12-MC-4 complex, and which corresponds to the metallacrown complex predicted by the Metallacrown Structural Paradigm. Besides this species, we have very unexpectedly identified in solution three other polynuclear species, corresponding to the stoichiometries [Ni4(LH(-1))4], [Ni5(LH(-1))5] and [Ni6(LH(-1))6]. A metallacrown with the same stoichiometry as [Ni5(LH(-1))5] containing α-AlaHA as the ligand has been previously reported, while the other two species are new for the speciation systems of Cu(II) or Ni(II) aminohydroxamic acids. Intriguingly, all the three latter stoichiometries correspond to those of vacant 12-MC-4, 15-MC-5 or 18-MC-6 species. The thermodynamic parameters related to their formation in solution are discussed, together with the speciation of the mononuclear complexes, on the basis of the structural and thermodynamic information available on metallacrowns.

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The new decanuclear copper(II) cluster [Cu5(β-alaha)4Cl2]2·2HCl·15H2O, its structure, spectroscopy and magnetism

Cited by 17 publications

References 31 publications

A Triple‐Decker Heptadecanuclear (Cu^II)₁₅(Cr^III)₂ Complex Assembled from Pentanuclear Metallacrowns

A Triple‐Decker Heptadecanuclear (Cu^II)₁₅(Cr^III)₂ Complex Assembled from Pentanuclear Metallacrowns

Supramolecular Maleate Adducts of Copper(II) 12‐Metallacrown‐4: Magnetism, EPR, and Alcohol Sorption Properties

Stoichiometric diversity of Ni(ii) metallacrowns with β-alaninehydroxamic acid in aqueous solution

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The new decanuclear copper(II) cluster [Cu5(β-alaha)4Cl2]2·2HCl·15H2O, its structure, spectroscopy and magnetism

Cited by 17 publications

References 31 publications

A Triple‐Decker Heptadecanuclear (CuII)15(CrIII)2 Complex Assembled from Pentanuclear Metallacrowns

A Triple‐Decker Heptadecanuclear (CuII)15(CrIII)2 Complex Assembled from Pentanuclear Metallacrowns

Supramolecular Maleate Adducts of Copper(II) 12‐Metallacrown‐4: Magnetism, EPR, and Alcohol Sorption Properties

Stoichiometric diversity of Ni(ii) metallacrowns with β-alaninehydroxamic acid in aqueous solution

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A Triple‐Decker Heptadecanuclear (Cu^II)₁₅(Cr^III)₂ Complex Assembled from Pentanuclear Metallacrowns

A Triple‐Decker Heptadecanuclear (Cu^II)₁₅(Cr^III)₂ Complex Assembled from Pentanuclear Metallacrowns