Covalent Co-O-V and Sb-N Bonds Enable Polyoxovanadate Charge Control

Maren Rasmussen; Christian Näther; Jan Van Leusen; Paul Kögerler; Lyuben Zhechkov; Thoma Heine; Wolfgang Bensch

doi:10.1021/acs.inorgchem.7b00724

Covalent Co-O-V and Sb-N Bonds Enable Polyoxovanadate Charge Control

Maren Rasmussen, Christian Näther, Jan Van Leusen, Paul Kögerler, Lyuben Zhechkov, Thoma Heine, Wolfgang Bensch

Department of Chemistry

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

14 Citations (Scopus)

Abstract

The formation of [{Co^II(teta)₂}{Co^II₂(tren)(teta)₂}V^IV₁₅Sb^III₆O₄₂(H₂O)]·ca.9H₂O [teta = triethylenetetraamine; tren = tris(2-aminoethyl)amine] illustrates a strategy toward reducing the molecular charge of polyoxovanadates, a key challenge in their use as components in single-molecule electronics. Here, a V-O-Co bond to a binuclear Co²⁺-centered complex and a Sb-N bond to the terminal N atom of a teta ligand of a mononuclear Co²⁺ complex allow for full charge compensation of the archetypal molecular magnet [V₁₅Sb₆O₄₂(H₂O)]^6-. Density functional theory based electron localization function analysis demonstrates that the Sb-N bond has an electron density similar to that of a Sb-O bond. Magnetic exchange coupling between the V^IV and Co^II spin centers mediated via the Sb-N bridge is comparably weakly antiferromagnetic.

Original language	English
Pages (from-to)	7120-7126
Number of pages	7
Journal	Inorganic Chemistry
Volume	56
Issue number	12
DOIs	https://doi.org/10.1021/acs.inorgchem.7b00724
Publication status	Published - 2017 Jun 19

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© 2017 American Chemical Society.

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.7b00724

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title = "Covalent Co-O-V and Sb-N Bonds Enable Polyoxovanadate Charge Control",

abstract = "The formation of [{CoII(teta)2}{CoII2(tren)(teta)2}VIV15SbIII6O42(H2O)]·ca.9H2O [teta = triethylenetetraamine; tren = tris(2-aminoethyl)amine] illustrates a strategy toward reducing the molecular charge of polyoxovanadates, a key challenge in their use as components in single-molecule electronics. Here, a V-O-Co bond to a binuclear Co2+-centered complex and a Sb-N bond to the terminal N atom of a teta ligand of a mononuclear Co2+ complex allow for full charge compensation of the archetypal molecular magnet [V15Sb6O42(H2O)]6-. Density functional theory based electron localization function analysis demonstrates that the Sb-N bond has an electron density similar to that of a Sb-O bond. Magnetic exchange coupling between the VIV and CoII spin centers mediated via the Sb-N bridge is comparably weakly antiferromagnetic.",

author = "Maren Rasmussen and Christian N{\"a}ther and {Van Leusen}, Jan and Paul K{\"o}gerler and Lyuben Zhechkov and Thoma Heine and Wolfgang Bensch",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

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doi = "10.1021/acs.inorgchem.7b00724",

language = "English",

volume = "56",

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T1 - Covalent Co-O-V and Sb-N Bonds Enable Polyoxovanadate Charge Control

AU - Rasmussen, Maren

AU - Näther, Christian

AU - Van Leusen, Jan

AU - Kögerler, Paul

AU - Zhechkov, Lyuben

AU - Heine, Thoma

AU - Bensch, Wolfgang

PY - 2017/6/19

Y1 - 2017/6/19

N2 - The formation of [{CoII(teta)2}{CoII2(tren)(teta)2}VIV15SbIII6O42(H2O)]·ca.9H2O [teta = triethylenetetraamine; tren = tris(2-aminoethyl)amine] illustrates a strategy toward reducing the molecular charge of polyoxovanadates, a key challenge in their use as components in single-molecule electronics. Here, a V-O-Co bond to a binuclear Co2+-centered complex and a Sb-N bond to the terminal N atom of a teta ligand of a mononuclear Co2+ complex allow for full charge compensation of the archetypal molecular magnet [V15Sb6O42(H2O)]6-. Density functional theory based electron localization function analysis demonstrates that the Sb-N bond has an electron density similar to that of a Sb-O bond. Magnetic exchange coupling between the VIV and CoII spin centers mediated via the Sb-N bridge is comparably weakly antiferromagnetic.

AB - The formation of [{CoII(teta)2}{CoII2(tren)(teta)2}VIV15SbIII6O42(H2O)]·ca.9H2O [teta = triethylenetetraamine; tren = tris(2-aminoethyl)amine] illustrates a strategy toward reducing the molecular charge of polyoxovanadates, a key challenge in their use as components in single-molecule electronics. Here, a V-O-Co bond to a binuclear Co2+-centered complex and a Sb-N bond to the terminal N atom of a teta ligand of a mononuclear Co2+ complex allow for full charge compensation of the archetypal molecular magnet [V15Sb6O42(H2O)]6-. Density functional theory based electron localization function analysis demonstrates that the Sb-N bond has an electron density similar to that of a Sb-O bond. Magnetic exchange coupling between the VIV and CoII spin centers mediated via the Sb-N bridge is comparably weakly antiferromagnetic.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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ER -

Covalent Co-O-V and Sb-N Bonds Enable Polyoxovanadate Charge Control

Abstract

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