Study of a novel hepta-coordinated FeIII bimetallic complex with an unusual 1,2,4,5-tetrazine-ring opening

Lemes, Maykon Alves; Pialat, Amélie; Steinmann, Stephan N.; Korobkov, Ilia; Michel, Carine; Murugesu, Muralee

doi:10.1016/j.poly.2015.11.024

Cited by 12 publications

(12 citation statements)

References 40 publications

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“…However, if O11 was changed to nitrogen during the refinement process, the observed thermal ellipsoids no longer gave reasonable parameters, indicating the element is most likely oxygen. The decomposition of the central tetrazine ring of bpztz is likely metal‐assisted, as similar behaviour has been observed in other 1,2,4,5‐tetrazine‐based ligand systems [15–22] . However, to the best of our knowledge, such an asymmetric ring opening not been previously observed in the presence of lanthanides.…”

Section: Resultssupporting

confidence: 83%

“…However, serendipitous transformation of the ligand might occur upon interaction with the metal centre. This is well highlighted in the family of 1,2,4,5‐tetrazine‐based ligands [15–22] . These molecules are of interest in coordination chemistry due to their facile functionalisation and their redox activity, which can enhance magnetic communication between metal ions [23–26] .…”

Section: Introductionmentioning

confidence: 97%

“…This is well highlighted in the family of 1,2,4,5-tetrazine-based ligands. [15][16][17][18][19][20][21][22] These molecules are of interesti nc oordination chemistry due to their facile functionalisationa nd their redoxa ctivity,w hich can enhancem agnetic communication between metal ions. [23][24][25][26] For these reasons, the quest for tetrazine-based compounds is an extremely activef ield of research in coordinationc hemistry.…”

Section: Introductionmentioning

confidence: 99%

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Asymmetric Ring Opening in a Tetrazine‐Based Ligand Affords a Tetranuclear Opto‐Magnetic Ytterbium Complex

Richardson

Marin

Zhang

et al. 2020

Chemistry A European J

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We report the formation of a tetranuclear lanthanide cluster, [Yb4(bpzch)2(fod)10] (1), which occurs from a serendipitous ring opening of the functionalised tetrazine bridging ligand, bpztz (3,6‐dipyrazin‐2‐yl‐1,2,4,5‐tetrazine) upon reacting with Yb(fod)3 (fod−=6,6,7,7,8,8,8‐heptafluoro‐2,2‐dimethyl‐3,5‐octandionate). Compound 1 was structurally elucidated via single‐crystal X‐ray crystallography and subsequently magnetically and spectroscopically characterised to analyse its magnetisation dynamics and its luminescence behaviour. Computational studies validate the observed MJ energy levels attained by spectroscopy and provides a clearer picture of the slow relaxation of the magnetisation dynamics and relaxation pathways. These studies demonstrate that 1 acts as a single‐molecule magnet (SMM) under an applied magnetic field in which the relaxation occurs via a combination of Raman, direct, and quantum tunnelling processes, a behaviour further rationalised analysing the luminescent properties. This marks the first lanthanide‐containing molecule that forms by means of an asymmetric tetrazine decomposition.

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Section: Resultssupporting

confidence: 83%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

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Asymmetric Ring Opening in a Tetrazine‐Based Ligand Affords a Tetranuclear Opto‐Magnetic Ytterbium Complex

Richardson

Marin

Zhang

et al. 2020

Chemistry A European J

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“…Indeed, under certain synthetic conditions, a metal-assisted ring opening of the tetrazine ring can be observed, leading to unpredicted structures. 4…”

Section: Introductionmentioning

confidence: 99%

Tetrazine-Based Ligand Transformation Driving Metal–Metal Bond and Mixed-Valence Hg^I/Hg^II

et al. 2018

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Understanding the self-assembly of cluster aggregates remains an important challenge in coordination chemistry. A chelating tetrazine-based ligand was employed to isolate an unprecedented tetranuclear Hg 4 complex exhibiting Hg I /Hg II mixed valence, which also contains metal–metal bonds. Single-crystal X-ray diffraction, X-ray photoelectron spectroscopy, solid-state nuclear magnetic resonance, and theoretical approaches (density functional theory) were employed to shed some light on the structure and self-assembly of this discrete molecule.

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“…In the compounds presented herein, we observe the spontaneous generation of a radical upon metal coordination, and under ambient conditions. Moreover, we have yet to encounter any 1,2,4,5-tetrazine-ring opening reactivity in BPyTz, which has been observed in a closely related 3,6-bis(2′-pyrimidyl) −1,2,4,5-tetrazine (BPymTz) organic ligand 26 . These features render the open-shell BPyTz •− ligand an ideal building block with which to facilitate and promote direct exchange coupling with lanthanide ions, despite deeply buried 4f orbitals.…”

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A tunable lanthanide cubane platform incorporating air-stable radical ligands for enhanced magnetic communication

et al. 2018

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The unique properties of polynuclear cluster-aggregates have long been staples in the molecular magnetism community. The initial success observed in high nuclearity transition metal complexes for generating exciting magnetic behaviors however, has not yet fully been extended to lanthanide-based clusters. This is in part due to the challenges related to promoting non-negligible magnetic interactions between two lanthanide ions. One promising route towards improving magnetic communication involves the incorporation of radical species. Here, we describe the preparation of tetranuclear [Dy 4 (μ 3-OH) 4 ] 8+ core structures that allow the incorporation of air-stable radical ligands. This combination paves the way for magnetically relevant lanthanide cubane cluster-aggregates capable of strong magnetic communication and improved spin-reversal barriers. Moreover, we show that the addition of electron donating groups lead to non-negligible antiferromagnetic coupling between the Dy III centers and the BPyTz •− ligands, while also simultaneously improving the slow magnetic relaxation dynamics in the absence of an applied field.

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Study of a novel hepta-coordinated FeIII bimetallic complex with an unusual 1,2,4,5-tetrazine-ring opening

Cited by 12 publications

References 40 publications

Asymmetric Ring Opening in a Tetrazine‐Based Ligand Affords a Tetranuclear Opto‐Magnetic Ytterbium Complex

Asymmetric Ring Opening in a Tetrazine‐Based Ligand Affords a Tetranuclear Opto‐Magnetic Ytterbium Complex

Tetrazine-Based Ligand Transformation Driving Metal–Metal Bond and Mixed-Valence Hg^I/Hg^II

A tunable lanthanide cubane platform incorporating air-stable radical ligands for enhanced magnetic communication

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Study of a novel hepta-coordinated FeIII bimetallic complex with an unusual 1,2,4,5-tetrazine-ring opening

Cited by 12 publications

References 40 publications

Asymmetric Ring Opening in a Tetrazine‐Based Ligand Affords a Tetranuclear Opto‐Magnetic Ytterbium Complex

Asymmetric Ring Opening in a Tetrazine‐Based Ligand Affords a Tetranuclear Opto‐Magnetic Ytterbium Complex

Tetrazine-Based Ligand Transformation Driving Metal–Metal Bond and Mixed-Valence HgI/HgII

A tunable lanthanide cubane platform incorporating air-stable radical ligands for enhanced magnetic communication

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Tetrazine-Based Ligand Transformation Driving Metal–Metal Bond and Mixed-Valence Hg^I/Hg^II