Stepwise substituting magnetic centres in a giant cluster host system

Achim Müller; Winfried Plass; Erich Krickemeyer; Roberta Sessoli; Dante Gatteschi; Jochen Meyer; Hartmut Bögge; Monika Kröckel; Alfred X. Trautwein

doi:10.1016/S0020-1693(97)05885-4

Stepwise substituting magnetic centres in a giant cluster host system

Achim Müller^*, Winfried Plass, Erich Krickemeyer, Roberta Sessoli, Dante Gatteschi, Jochen Meyer, Hartmut Bögge, Monika Kröckel, Alfred X. Trautwein

^*Korrespondierende/r Autor/-in für diese Arbeit

Institut für Physik

25 Zitate (Scopus)

Abstract

In the polyoxomolybdate shell of the cluster compound (NH₄)₂₁[{V^IVO(H₂O)} ₆{Mo(μ-H₂O)₂(μ-OH)Mo}₃{Mo ₁₅(MoNO)₂-O₅₈(H₂O)₂} ₃] ([V₆]), {Fe^III(H₂O)₂} and {Fe^II(H₂O)₂} moieties can be incorporated at the positions of the {VO(H₂O)} groups. On adding FeCl₃·6H₂O in excess to a solution from which pure [V₆] can be isolated, the cluster compound (NH₄)₁₅[{Fe^III(H₂O) ₂}₆{Mo(μ-H₂O)₂-(μ-OH)Mo} ₃{MO₁₅(MoNO)₂O₅₈(H ₂O)₂}₃] ([Fe₆]) is formed. By adding varying amounts of FeCl₂·4H₂O or FeCl₃·6H₂O to such a solution, a series of compounds can be isolated with different ratios of oxovanadium(IV), iron(III), and iron(II) centres. The experimental conditions allow tuning of these ratios in the prepared compounds, 〈V₄Fe₂〉, 〈V₃Fe₃〉, 〈V₂Fe₄〉 and 〈VFe₅〉 with varying iron(III) / iron(II) ratio (depending on the degree of oxidation of iron(II) centres) and 〈VFe^III ₅〉. These formulae correspond to those of [V₆] and [Fe₆] with the relevant intermediate NH₄ ⁺ content. The synthesized compounds were characterized by elemental analyses, different spectroscopic methods, and X-ray crystal structure analyses as well as ⁵⁷Fe-Mößbauer spectroscopy which allowed determination of the iron(III) / iron(II) ratio. The magnetic properties of all cluster compounds were carefully investigated. For one of the mixed systems an interesting ferrimagnetic behaviour is observed and can only be explained if the different magnetic centres occur within a single cluster shell and are not separated in different clusters.

Originalsprache	Englisch
Zeitschrift	Inorganica Chimica Acta
Jahrgang	271
Ausgabenummer	1-2
Seiten (von - bis)	9-12
Seitenumfang	4
ISSN	0020-1693
DOIs	https://doi.org/10.1016/S0020-1693(97)05885-4
Publikationsstatus	Veröffentlicht - 15.04.1998

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@article{3c95ba52e68440e98b92dd7fb5c2dfd1,

title = "Stepwise substituting magnetic centres in a giant cluster host system",

abstract = "In the polyoxomolybdate shell of the cluster compound (NH4)21[{VIVO(H2O)} 6{Mo(μ-H2O)2(μ-OH)Mo}3{Mo 15(MoNO)2-O58(H2O)2} 3] ([V6]), {FeIII(H2O)2} and {FeII(H2O)2} moieties can be incorporated at the positions of the {VO(H2O)} groups. On adding FeCl3·6H2O in excess to a solution from which pure [V6] can be isolated, the cluster compound (NH4)15[{FeIII(H2O) 2}6{Mo(μ-H2O)2-(μ-OH)Mo} 3{MO15(MoNO)2O58(H 2O)2}3] ([Fe6]) is formed. By adding varying amounts of FeCl2·4H2O or FeCl3·6H2O to such a solution, a series of compounds can be isolated with different ratios of oxovanadium(IV), iron(III), and iron(II) centres. The experimental conditions allow tuning of these ratios in the prepared compounds, 〈V4Fe2〉, 〈V3Fe3〉, 〈V2Fe4〉 and 〈VFe5〉 with varying iron(III) / iron(II) ratio (depending on the degree of oxidation of iron(II) centres) and 〈VFeIII 5〉. These formulae correspond to those of [V6] and [Fe6] with the relevant intermediate NH4 + content. The synthesized compounds were characterized by elemental analyses, different spectroscopic methods, and X-ray crystal structure analyses as well as 57Fe-M{\"o}{\ss}bauer spectroscopy which allowed determination of the iron(III) / iron(II) ratio. The magnetic properties of all cluster compounds were carefully investigated. For one of the mixed systems an interesting ferrimagnetic behaviour is observed and can only be explained if the different magnetic centres occur within a single cluster shell and are not separated in different clusters.",

author = "Achim M{\"u}ller and Winfried Plass and Erich Krickemeyer and Roberta Sessoli and Dante Gatteschi and Jochen Meyer and Hartmut B{\"o}gge and Monika Kr{\"o}ckel and Trautwein, {Alfred X.}",

year = "1998",

month = apr,

day = "15",

doi = "10.1016/S0020-1693(97)05885-4",

language = "English",

volume = "271",

pages = "9--12",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

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T1 - Stepwise substituting magnetic centres in a giant cluster host system

AU - Müller, Achim

AU - Plass, Winfried

AU - Krickemeyer, Erich

AU - Sessoli, Roberta

AU - Gatteschi, Dante

AU - Meyer, Jochen

AU - Bögge, Hartmut

AU - Kröckel, Monika

AU - Trautwein, Alfred X.

PY - 1998/4/15

Y1 - 1998/4/15

N2 - In the polyoxomolybdate shell of the cluster compound (NH4)21[{VIVO(H2O)} 6{Mo(μ-H2O)2(μ-OH)Mo}3{Mo 15(MoNO)2-O58(H2O)2} 3] ([V6]), {FeIII(H2O)2} and {FeII(H2O)2} moieties can be incorporated at the positions of the {VO(H2O)} groups. On adding FeCl3·6H2O in excess to a solution from which pure [V6] can be isolated, the cluster compound (NH4)15[{FeIII(H2O) 2}6{Mo(μ-H2O)2-(μ-OH)Mo} 3{MO15(MoNO)2O58(H 2O)2}3] ([Fe6]) is formed. By adding varying amounts of FeCl2·4H2O or FeCl3·6H2O to such a solution, a series of compounds can be isolated with different ratios of oxovanadium(IV), iron(III), and iron(II) centres. The experimental conditions allow tuning of these ratios in the prepared compounds, 〈V4Fe2〉, 〈V3Fe3〉, 〈V2Fe4〉 and 〈VFe5〉 with varying iron(III) / iron(II) ratio (depending on the degree of oxidation of iron(II) centres) and 〈VFeIII 5〉. These formulae correspond to those of [V6] and [Fe6] with the relevant intermediate NH4 + content. The synthesized compounds were characterized by elemental analyses, different spectroscopic methods, and X-ray crystal structure analyses as well as 57Fe-Mößbauer spectroscopy which allowed determination of the iron(III) / iron(II) ratio. The magnetic properties of all cluster compounds were carefully investigated. For one of the mixed systems an interesting ferrimagnetic behaviour is observed and can only be explained if the different magnetic centres occur within a single cluster shell and are not separated in different clusters.

AB - In the polyoxomolybdate shell of the cluster compound (NH4)21[{VIVO(H2O)} 6{Mo(μ-H2O)2(μ-OH)Mo}3{Mo 15(MoNO)2-O58(H2O)2} 3] ([V6]), {FeIII(H2O)2} and {FeII(H2O)2} moieties can be incorporated at the positions of the {VO(H2O)} groups. On adding FeCl3·6H2O in excess to a solution from which pure [V6] can be isolated, the cluster compound (NH4)15[{FeIII(H2O) 2}6{Mo(μ-H2O)2-(μ-OH)Mo} 3{MO15(MoNO)2O58(H 2O)2}3] ([Fe6]) is formed. By adding varying amounts of FeCl2·4H2O or FeCl3·6H2O to such a solution, a series of compounds can be isolated with different ratios of oxovanadium(IV), iron(III), and iron(II) centres. The experimental conditions allow tuning of these ratios in the prepared compounds, 〈V4Fe2〉, 〈V3Fe3〉, 〈V2Fe4〉 and 〈VFe5〉 with varying iron(III) / iron(II) ratio (depending on the degree of oxidation of iron(II) centres) and 〈VFeIII 5〉. These formulae correspond to those of [V6] and [Fe6] with the relevant intermediate NH4 + content. The synthesized compounds were characterized by elemental analyses, different spectroscopic methods, and X-ray crystal structure analyses as well as 57Fe-Mößbauer spectroscopy which allowed determination of the iron(III) / iron(II) ratio. The magnetic properties of all cluster compounds were carefully investigated. For one of the mixed systems an interesting ferrimagnetic behaviour is observed and can only be explained if the different magnetic centres occur within a single cluster shell and are not separated in different clusters.

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U2 - 10.1016/S0020-1693(97)05885-4

DO - 10.1016/S0020-1693(97)05885-4

M3 - Journal articles

AN - SCOPUS:0038425974

SN - 0020-1693

VL - 271

SP - 9

EP - 12

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 1-2

ER -

Stepwise substituting magnetic centres in a giant cluster host system

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