Construction of a mixed-valence Mn16 cluster with four tetrahedrons

Wang, Feng; Fu, Zhengbing; Guo, Liangui; Du, Jun; Ding, Yu

doi:10.1016/j.inoche.2016.10.024

Cited by 2 publications

(2 citation statements)

References 31 publications

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“…The average magnetic interaction is fairly considerable and antiferromagnetic. However, by considering the geometries and applying Goodenough–Kanamori rule, as well as referring to known examples in the literature, ,, we note that the double-oxygen bridge of the two Mn(III) with a Mn III –O–Mn III of 81° is considered to be ferromagnetic (F), while all the other single-oxygen bridge connections with Mn–O–Mn angles of 123 ± 1° are antiferromagnetic (AF). Since in general ferromagnetic exchange is weaker than antiferromagnetic one, the susceptibility appears dominated by the AF ones.…”

Section: Resultsmentioning

confidence: 99%

Hexadecanuclear Mn^II₂Mn^III₁₄ Molecular Torus Built from in Situ Tandem Ligand Transformations

Riaz

Gupta

et al. 2019

Inorg. Chem.

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14 (trz) 14 (thetach) 4 (μ 3 -O) 8 (H 2 O) 10 ](ClO 4 ) 6 (Mn16), containing two Mn II and 14 Mn III ions, is constructed from mixed in situ generated ligands, 1,2,3-triazole (Htrz) and 1,3,5-tri(2-hydroxyethyl)-1,3,5-triazacyclohexane (H 3 thetach). Remarkably, both ligands were not initially added into the reaction system, and their formations involve the in situ ligand decomposition and subsequent condensation reactions. The core of Mn16 is an elongated torus comprised of eight Mn atoms and four [Mn 2 O 2 ] subunits bridged by oxo or alkoxide. The high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) of Mn16 dissolved in CH 3 CN indicates its structure remains intact as +3 and +4 species. Temperature and field dependent magnetization revealed predominantly antiferromagnetic exchange interactions within the cluster. The work provides one-pot synthesis of high-nuclearity manganese clusters using the ligands generated by in situ reactions in a tandem fashion.

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Section: Resultsmentioning

confidence: 99%

Hexadecanuclear Mn^II₂Mn^III₁₄ Molecular Torus Built from in Situ Tandem Ligand Transformations

Riaz

Gupta

et al. 2019

Inorg. Chem.

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“…We expect similar patterns would also arise in many other mixed‐valence systems . A clear visualization of such induced α/β‐density heap may give insights in the study of structures like molecular wires or clusters . In addition, there are a lot of reactions in which spin‐polarized species have been involved, especially in first‐row transition metal catalyzed reactions, N 2 cleavage reactions, proton‐coupled electron transfer, and O 2 ‐involving reactions .…”

Section: Resultsmentioning

confidence: 62%

Revitalizing Spin Natural Orbital Analysis: Electronic Structures of Mixed‐Valence Compounds, Singlet Biradicals, and Antiferromagnetically Coupled Systems

2019

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Chemical systems with open-shell electronic structure have been gaining attention these days. Their potential applications in firstrow transition metal catalysis, molecular wires, photovoltaics and other potential applications have urged the adoption of a simple analysis tool to better understand their open-shell electronic structures, especially the role played by the unpaired electrons. Despite its lack of popularity, spin natural orbital (SNO) analysis is a tool we found to well-suit this purpose. We have therefore re-examined how the SNO could help us analyze some interesting open-shell systems, including mixed-valence compounds, singlet biradicals, and antiferromagnetically coupled systems. We found that some interesting patterns emerge from SNO analysis, especially those associated with exchange interaction.The SNO analysis, the main method we wish to discuss in this article, approaches the "correspondence" problem from a different angle. Although at the first glance the definition does not suggest a correspondence relationship, we will present its intimate connection with the COT and why it will always give such correspondence in a single-determinant calculation.

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Construction of a mixed-valence Mn16 cluster with four tetrahedrons

Cited by 2 publications

References 31 publications

Hexadecanuclear Mn^II₂Mn^III₁₄ Molecular Torus Built from in Situ Tandem Ligand Transformations

Hexadecanuclear Mn^II₂Mn^III₁₄ Molecular Torus Built from in Situ Tandem Ligand Transformations

Revitalizing Spin Natural Orbital Analysis: Electronic Structures of Mixed‐Valence Compounds, Singlet Biradicals, and Antiferromagnetically Coupled Systems

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Construction of a mixed-valence Mn16 cluster with four tetrahedrons

Cited by 2 publications

References 31 publications

Hexadecanuclear MnII2MnIII14 Molecular Torus Built from in Situ Tandem Ligand Transformations

Hexadecanuclear MnII2MnIII14 Molecular Torus Built from in Situ Tandem Ligand Transformations

Revitalizing Spin Natural Orbital Analysis: Electronic Structures of Mixed‐Valence Compounds, Singlet Biradicals, and Antiferromagnetically Coupled Systems

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Hexadecanuclear Mn^II₂Mn^III₁₄ Molecular Torus Built from in Situ Tandem Ligand Transformations

Hexadecanuclear Mn^II₂Mn^III₁₄ Molecular Torus Built from in Situ Tandem Ligand Transformations