Modular [FeIII8MII6]n+ (MII = Pd, Co, Ni, Cu) Coordination Cages

Sergio Sanz; Helen M. O’Connor; Priyanka Comar; Amgalanbaatar Baldansuren; Mateusz B. Pitak; Simon J. Coles; Høgni Weihe; Nicholas F. Chilton; Eric J. L. McInnes; Paul J. Lusby; Stergios Piligkos; Euan K. Brechin

doi:10.1021/acs.inorgchem.7b02674

Modular [Fe^III₈M^II₆]ⁿ⁺(M^II = Pd, Co, Ni, Cu) Coordination Cages

Sergio Sanz^*, Helen M. O’Connor, Priyanka Comar, Amgalanbaatar Baldansuren, Mateusz B. Pitak, Simon J. Coles, Høgni Weihe, Nicholas F. Chilton, Eric J. L. McInnes, Paul J. Lusby^*, Stergios Piligkos^*, Euan K. Brechin^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

16 Citations (Scopus)

Abstract

The reaction of the simple metalloligand [Fe^IIIL₃] [HL = 1-(4-pyridyl)butane-1,3-dione] with a variety of different M^II salts results in the formation of a family of heterometallic cages of formulae [Fe^III₈Pd^II₆L²⁴]Cl₁₂ (1), [Fe^III₈Cu^II₆L₂₄(H₂O)₄Br₄]Br₈ (2), [Fe^III₈Cu^II₆L₂₄(H₂O)₁₀](NO₃)₁₂ (3), [Fe^III₈Ni^II₆L₂₄(SCN)₁₁Cl] (4), and [Fe^III₈Co^II₆L₂₄(SCN)₁₀(H₂O)₂]Cl₂ (5). The metallic skeleton of each cage describes a cube in which the FeIII ions occupy the eight vertices and the MII ions lie at the center of the six faces. Direct-current magnetic susceptibility and magnetization measurements on 3–5 reveal the presence of weak antiferromagnetic exchange between the metal ions in all three cases. Computational techniques known in theoretical nuclear physics as statistical spectroscopy, which exploit the moments of the Hamiltonian to calculate relevant thermodynamic properties, determine J_Fe–Cu = 0.10 cm^–1 for 3 and J_Fe–Ni = 0.025 cm^–1 for 4. Q-band electron paramagnetic resonance spectra of 1 reveal a significantly wider spectral width in comparison to [FeL₃], indicating that the magnitude of the Fe^III zero-field splitting is larger in the heterometallic cage than in the monomer.

Original language	English
Pages (from-to)	3500-3506
Number of pages	7
Journal	Inorganic Chemistry
Volume	57
Issue number	7
DOIs	https://doi.org/10.1021/acs.inorgchem.7b02674
Publication status	Published - 11 Jan 2018
Externally published	Yes

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10.1021/acs.inorgchem.7b02674

https://pubs.acs.org/doi/10.1021/acs.inorgchem.7b02674

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@article{60112326d429480d9fbe34d43286c4ec,

title = "Modular [FeIII8MII6]n+ (MII = Pd, Co, Ni, Cu) Coordination Cages",

abstract = "The reaction of the simple metalloligand [FeIIIL3] [HL = 1-(4-pyridyl)butane-1,3-dione] with a variety of different MII salts results in the formation of a family of heterometallic cages of formulae [FeIII8PdII6L24]Cl12 (1), [FeIII8CuII6L24(H2O)4Br4]Br8 (2), [FeIII8CuII6L24(H2O)10](NO3)12 (3), [FeIII8NiII6L24(SCN)11Cl] (4), and [FeIII8CoII6L24(SCN)10(H2O)2]Cl2 (5). The metallic skeleton of each cage describes a cube in which the FeIII ions occupy the eight vertices and the MII ions lie at the center of the six faces. Direct-current magnetic susceptibility and magnetization measurements on 3–5 reveal the presence of weak antiferromagnetic exchange between the metal ions in all three cases. Computational techniques known in theoretical nuclear physics as statistical spectroscopy, which exploit the moments of the Hamiltonian to calculate relevant thermodynamic properties, determine JFe–Cu = 0.10 cm–1 for 3 and JFe–Ni = 0.025 cm–1 for 4. Q-band electron paramagnetic resonance spectra of 1 reveal a significantly wider spectral width in comparison to [FeL3], indicating that the magnitude of the FeIII zero-field splitting is larger in the heterometallic cage than in the monomer.",

author = "Sergio Sanz and O{\textquoteright}Connor, {Helen M.} and Priyanka Comar and Amgalanbaatar Baldansuren and Pitak, {Mateusz B.} and Coles, {Simon J.} and H{\o}gni Weihe and Chilton, {Nicholas F.} and McInnes, {Eric J. L.} and Lusby, {Paul J.} and Stergios Piligkos and Brechin, {Euan K.}",

year = "2018",

month = jan,

day = "11",

doi = "10.1021/acs.inorgchem.7b02674",

language = "English",

volume = "57",

pages = "3500--3506",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "7",

}

TY - JOUR

T1 - Modular [FeIII8MII6]n+ (MII = Pd, Co, Ni, Cu) Coordination Cages

AU - Sanz, Sergio

AU - O’Connor, Helen M.

AU - Comar, Priyanka

AU - Baldansuren, Amgalanbaatar

AU - Pitak, Mateusz B.

AU - Coles, Simon J.

AU - Weihe, Høgni

AU - Chilton, Nicholas F.

AU - McInnes, Eric J. L.

AU - Lusby, Paul J.

AU - Piligkos, Stergios

AU - Brechin, Euan K.

PY - 2018/1/11

Y1 - 2018/1/11

N2 - The reaction of the simple metalloligand [FeIIIL3] [HL = 1-(4-pyridyl)butane-1,3-dione] with a variety of different MII salts results in the formation of a family of heterometallic cages of formulae [FeIII8PdII6L24]Cl12 (1), [FeIII8CuII6L24(H2O)4Br4]Br8 (2), [FeIII8CuII6L24(H2O)10](NO3)12 (3), [FeIII8NiII6L24(SCN)11Cl] (4), and [FeIII8CoII6L24(SCN)10(H2O)2]Cl2 (5). The metallic skeleton of each cage describes a cube in which the FeIII ions occupy the eight vertices and the MII ions lie at the center of the six faces. Direct-current magnetic susceptibility and magnetization measurements on 3–5 reveal the presence of weak antiferromagnetic exchange between the metal ions in all three cases. Computational techniques known in theoretical nuclear physics as statistical spectroscopy, which exploit the moments of the Hamiltonian to calculate relevant thermodynamic properties, determine JFe–Cu = 0.10 cm–1 for 3 and JFe–Ni = 0.025 cm–1 for 4. Q-band electron paramagnetic resonance spectra of 1 reveal a significantly wider spectral width in comparison to [FeL3], indicating that the magnitude of the FeIII zero-field splitting is larger in the heterometallic cage than in the monomer.

AB - The reaction of the simple metalloligand [FeIIIL3] [HL = 1-(4-pyridyl)butane-1,3-dione] with a variety of different MII salts results in the formation of a family of heterometallic cages of formulae [FeIII8PdII6L24]Cl12 (1), [FeIII8CuII6L24(H2O)4Br4]Br8 (2), [FeIII8CuII6L24(H2O)10](NO3)12 (3), [FeIII8NiII6L24(SCN)11Cl] (4), and [FeIII8CoII6L24(SCN)10(H2O)2]Cl2 (5). The metallic skeleton of each cage describes a cube in which the FeIII ions occupy the eight vertices and the MII ions lie at the center of the six faces. Direct-current magnetic susceptibility and magnetization measurements on 3–5 reveal the presence of weak antiferromagnetic exchange between the metal ions in all three cases. Computational techniques known in theoretical nuclear physics as statistical spectroscopy, which exploit the moments of the Hamiltonian to calculate relevant thermodynamic properties, determine JFe–Cu = 0.10 cm–1 for 3 and JFe–Ni = 0.025 cm–1 for 4. Q-band electron paramagnetic resonance spectra of 1 reveal a significantly wider spectral width in comparison to [FeL3], indicating that the magnitude of the FeIII zero-field splitting is larger in the heterometallic cage than in the monomer.

U2 - 10.1021/acs.inorgchem.7b02674

DO - 10.1021/acs.inorgchem.7b02674

M3 - Article

SN - 0020-1669

VL - 57

SP - 3500

EP - 3506

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 7

ER -

Modular [FeIII8MII6]n+ (MII = Pd, Co, Ni, Cu) Coordination Cages

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Modular [Fe^III₈M^II₆]ⁿ⁺(M^II = Pd, Co, Ni, Cu) Coordination Cages