Synthesis and characterisation of new Ni2Mn, Ni2Mn2 and Mn8 clusters by the use of 2-pyridyl oximes

Constantinos G. Efthymiou; Ioannis Mylonas-Margaritis; S. Das Gupta; Anastasios Tasiopoulos; Vassilios Nastopoulos; George Christou; Spyros P. Perlepes; Constantina Papatriantafyllopoulou

doi:10.1016/j.poly.2019.07.024

Synthesis and characterisation of new Ni₂Mn, Ni₂Mn₂ and Mn₈ clusters by the use of 2-pyridyl oximes

Constantinos G. Efthymiou, Ioannis Mylonas-Margaritis, S. Das Gupta, Anastasios Tasiopoulos, Vassilios Nastopoulos, George Christou, Spyros P. Perlepes, Constantina Papatriantafyllopoulou

Cellular & Molecular Medicine

Research output: Contribution to a Journal (Peer & Non Peer) › Article › peer-review

6 Citations (Scopus)

Abstract

The initial employment of methyl 2-pyridyl ketoxime, (py)C(Me)NOH, in mixed metal Ni/Mn cluster chemistry, provided access to complexes [Ni^II₂Mn^III{(py)C(Me)NO}₆](ClO₄) (1) and [Ni^II₂Mn^III₂{(py)C(Me)NO}₆(OMe)₂(MeOH)₂](ClO₄)₂ (2) that display a linear and a zig-zag metal arrangement, respectively. 1 and 2 are synthesized by reacting Ni(ClO₄)₂·6H₂O, (py)C(Me)NOH, Mn(ClO₄)₂·6H₂O and NaOMe in different molar ratios (2:6:1:6, 1; 1:3:1:3, 2) in MeOH, and they are the first examples of 3d–3d′ mixed-metal clusters bearing (py)C(Me)NOH. The employment of phenyl 2-pyridyl ketoxime, (py)C(ph)NOH, instead of (py)C(Me)NOH, provided access to the octanuclear homometallic compound [Mn^II₄Mn^III₄O₄(NO₃)₂{(py)C(ph)NO}₈(HCO₂)₂(MeOH)₂] (3) that possesses a double-butterfly {Mn^II₄Mn^III₄(μ₄-O)₂(μ₃-O)₂}¹²⁺ core. 3 joins the small family of Mn/(py)C(ph)NO⁻ clusters. Variable-temperature, solid-state dc and ac magnetic susceptibility studies were carried out on 1 and 2 and revealed the presence of antiferromagnetic exchange interactions between the metal ions (J_Mn–Ni = −6.34 ± 0.14 cm⁻¹ in 1; J_Mn–Ni = −4.57 ± 0.08 cm⁻¹, J_Mn–Mn = −12.72 ± 0.12 in 2) and a diamagnetic ground state for both compounds.

Original language	English
Pages (from-to)	330-337
Number of pages	8
Journal	Polyhedron
Volume	171
DOIs	https://doi.org/10.1016/j.poly.2019.07.024
Publication status	Published - 1 Oct 2019

Keywords

2-Pyridyl oximes
3d–3d′ mixed metal clusters
Crystal structures
Magnetism
Ni/Mn compounds

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10.1016/j.poly.2019.07.024

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@article{33af00797ec748218df85976242b3146,

title = "Synthesis and characterisation of new Ni2Mn, Ni2Mn2 and Mn8 clusters by the use of 2-pyridyl oximes",

abstract = "The initial employment of methyl 2-pyridyl ketoxime, (py)C(Me)NOH, in mixed metal Ni/Mn cluster chemistry, provided access to complexes [NiII2MnIII\{(py)C(Me)NO\}6](ClO4) (1) and [NiII2MnIII2\{(py)C(Me)NO\}6(OMe)2(MeOH)2](ClO4)2 (2) that display a linear and a zig-zag metal arrangement, respectively. 1 and 2 are synthesized by reacting Ni(ClO4)2·6H2O, (py)C(Me)NOH, Mn(ClO4)2·6H2O and NaOMe in different molar ratios (2:6:1:6, 1; 1:3:1:3, 2) in MeOH, and they are the first examples of 3d–3d′ mixed-metal clusters bearing (py)C(Me)NOH. The employment of phenyl 2-pyridyl ketoxime, (py)C(ph)NOH, instead of (py)C(Me)NOH, provided access to the octanuclear homometallic compound [MnII4MnIII4O4(NO3)2\{(py)C(ph)NO\}8(HCO2)2(MeOH)2] (3) that possesses a double-butterfly \{MnII4MnIII4(μ4-O)2(μ3-O)2\}12+ core. 3 joins the small family of Mn/(py)C(ph)NO− clusters. Variable-temperature, solid-state dc and ac magnetic susceptibility studies were carried out on 1 and 2 and revealed the presence of antiferromagnetic exchange interactions between the metal ions (JMn–Ni = −6.34 ± 0.14 cm−1 in 1; JMn–Ni = −4.57 ± 0.08 cm−1, JMn–Mn = −12.72 ± 0.12 in 2) and a diamagnetic ground state for both compounds.",

keywords = "2-Pyridyl oximes, 3d–3d′ mixed metal clusters, Crystal structures, Magnetism, Ni/Mn compounds",

author = "Efthymiou, \{Constantinos G.\} and Ioannis Mylonas-Margaritis and \{Das Gupta\}, S. and Anastasios Tasiopoulos and Vassilios Nastopoulos and George Christou and Perlepes, \{Spyros P.\} and Constantina Papatriantafyllopoulou",

note = "Publisher Copyright: {\textcopyright} 2019 Elsevier Ltd",

year = "2019",

month = oct,

day = "1",

doi = "10.1016/j.poly.2019.07.024",

language = "English",

volume = "171",

pages = "330--337",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd",

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TY - JOUR

T1 - Synthesis and characterisation of new Ni2Mn, Ni2Mn2 and Mn8 clusters by the use of 2-pyridyl oximes

AU - Efthymiou, Constantinos G.

AU - Mylonas-Margaritis, Ioannis

AU - Das Gupta, S.

AU - Tasiopoulos, Anastasios

AU - Nastopoulos, Vassilios

AU - Christou, George

AU - Perlepes, Spyros P.

AU - Papatriantafyllopoulou, Constantina

PY - 2019/10/1

Y1 - 2019/10/1

N2 - The initial employment of methyl 2-pyridyl ketoxime, (py)C(Me)NOH, in mixed metal Ni/Mn cluster chemistry, provided access to complexes [NiII2MnIII{(py)C(Me)NO}6](ClO4) (1) and [NiII2MnIII2{(py)C(Me)NO}6(OMe)2(MeOH)2](ClO4)2 (2) that display a linear and a zig-zag metal arrangement, respectively. 1 and 2 are synthesized by reacting Ni(ClO4)2·6H2O, (py)C(Me)NOH, Mn(ClO4)2·6H2O and NaOMe in different molar ratios (2:6:1:6, 1; 1:3:1:3, 2) in MeOH, and they are the first examples of 3d–3d′ mixed-metal clusters bearing (py)C(Me)NOH. The employment of phenyl 2-pyridyl ketoxime, (py)C(ph)NOH, instead of (py)C(Me)NOH, provided access to the octanuclear homometallic compound [MnII4MnIII4O4(NO3)2{(py)C(ph)NO}8(HCO2)2(MeOH)2] (3) that possesses a double-butterfly {MnII4MnIII4(μ4-O)2(μ3-O)2}12+ core. 3 joins the small family of Mn/(py)C(ph)NO− clusters. Variable-temperature, solid-state dc and ac magnetic susceptibility studies were carried out on 1 and 2 and revealed the presence of antiferromagnetic exchange interactions between the metal ions (JMn–Ni = −6.34 ± 0.14 cm−1 in 1; JMn–Ni = −4.57 ± 0.08 cm−1, JMn–Mn = −12.72 ± 0.12 in 2) and a diamagnetic ground state for both compounds.

AB - The initial employment of methyl 2-pyridyl ketoxime, (py)C(Me)NOH, in mixed metal Ni/Mn cluster chemistry, provided access to complexes [NiII2MnIII{(py)C(Me)NO}6](ClO4) (1) and [NiII2MnIII2{(py)C(Me)NO}6(OMe)2(MeOH)2](ClO4)2 (2) that display a linear and a zig-zag metal arrangement, respectively. 1 and 2 are synthesized by reacting Ni(ClO4)2·6H2O, (py)C(Me)NOH, Mn(ClO4)2·6H2O and NaOMe in different molar ratios (2:6:1:6, 1; 1:3:1:3, 2) in MeOH, and they are the first examples of 3d–3d′ mixed-metal clusters bearing (py)C(Me)NOH. The employment of phenyl 2-pyridyl ketoxime, (py)C(ph)NOH, instead of (py)C(Me)NOH, provided access to the octanuclear homometallic compound [MnII4MnIII4O4(NO3)2{(py)C(ph)NO}8(HCO2)2(MeOH)2] (3) that possesses a double-butterfly {MnII4MnIII4(μ4-O)2(μ3-O)2}12+ core. 3 joins the small family of Mn/(py)C(ph)NO− clusters. Variable-temperature, solid-state dc and ac magnetic susceptibility studies were carried out on 1 and 2 and revealed the presence of antiferromagnetic exchange interactions between the metal ions (JMn–Ni = −6.34 ± 0.14 cm−1 in 1; JMn–Ni = −4.57 ± 0.08 cm−1, JMn–Mn = −12.72 ± 0.12 in 2) and a diamagnetic ground state for both compounds.

KW - 2-Pyridyl oximes

KW - 3d–3d′ mixed metal clusters

KW - Crystal structures

KW - Magnetism

KW - Ni/Mn compounds

UR - https://www.scopus.com/pages/publications/85070227317

U2 - 10.1016/j.poly.2019.07.024

DO - 10.1016/j.poly.2019.07.024

M3 - Article

SN - 0277-5387

VL - 171

SP - 330

EP - 337

JO - Polyhedron

JF - Polyhedron

ER -

Synthesis and characterisation of new Ni₂Mn, Ni₂Mn₂ and Mn₈ clusters by the use of 2-pyridyl oximes

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Keywords

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