Use of 155Gd, 151Eu, 166Er Mössbauer spectroscopy to characterize heterodinuclear Ln–Ln′ complexes

Costes, Jean‐Pierre; Nicodème, Franck; Ayabe, Takanari; Takeda, M.; Takahashi, Miwa

doi:10.1016/j.poly.2019.114154

Cited by 4 publications

(2 citation statements)

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“…scrambling). [66][67][68][69] Thus, examples of pure heterometallic Ln complexes remain rare. These are almost solely limited to phthalocyanine [70][71][72][73] and DOTA complexes.…”

Section: Introductionmentioning

confidence: 99%

Design of pure heterodinuclear lanthanoid cryptate complexes

et al. 2021

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“…scrambling). [66][67][68][69] Thus, examples of pure heterometallic Ln complexes remain rare. These are almost solely limited to phthalocyanine [70][71][72][73] and DOTA complexes.…”

Section: Introductionmentioning

confidence: 99%

Design of pure heterodinuclear lanthanoid cryptate complexes

et al. 2021

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“…scrambling). [66][67][68][69] Thus, examples of pure heterometallic Ln complexes remain rare. These are almost solely limited to phthalocyanine [70][71][72][73] and DOTA complexes.…”

mentioning

confidence: 99%

Design of Pure Heterodinuclear Lanthanoid Cryptate Complexes

Buch¹,

Hansen²,

Mitcov³

et al. 2021

Preprint

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Heterolanthanide complexes are difficult to synthesize owing to the similar chemistry of the lanthanide ions. Conse-quently, very few purely heterolanthanide complexes have been synthesized. This is despite the fact that such complexes hold inter-esting optical and magnetic properties. To fine-tune these properties, it is important that one can choose complexes with any given combination of lanthanides. Herein we report a synthetic procedure which yields pure heterodinuclear lanthanide cryptates LnLn*LX3 (X = NO3- or OTf-) based on the cryptand H3L = N[(CH2)2N=CH-R-CH=N-(CH2)2]3N (R = m-C6H2OH-2-Me-5). In the synthesis the choice of counter ion and solvent prove crucial in controlling the Ln-Ln*composition. Choosing the optimal solvent and counter ion affords pure heterodinuclear complexes with any given combination of Gd(III)-Lu(III) including Y(III). To demon-strate the versatility of the synthesis all dinuclear combinations of Y(III), Gd(III), Yb(III) and Lu(III) were synthesized resulting in 10 novel complexes of the form LnLn*L(OTf)3 with LnLn* = YbGd 1, YbY 2, YbLu 3, YbYb 4, LuGd 5, LuY 6, LuLu 7, YGd 8, YY 9 and GdGd 10. Through the use of 1H, 13C NMR and mass spectrometry the heterodinuclear nature of YbGd, YbY, YbLu, LuGd, LuY and YGd was confirmed. Crystal structures of LnLn*L(NO3)3 reveal short Ln-Ln distances of ~3.5 Å. Using SQUID magnetometry the exchange coupling between the lanthanide ions was found to be anti-ferromagnetic for GdGd and YbYb while ferromagnetic for YbGd.

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Heterodinuclear Transition‐Metal Complexes: Fundamentals, Synthesis, and Applications

Koessler

Butschke

2021

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Heterodinuclear transition‐metal complexes, that is coordination compounds comprising two different transition‐metal atoms, witness growing interest. This development is driven by the incentive to find complexes, which outperform their mononuclear competitors in reactivity and selectivity. It is particularly the close proximity of the two transition‐metal atoms, which promises to promote these favorable interactions denoted as “cooperative”. Therefore, mainly dinuclear complexes with direct metal–metal bonds are discussed in this article. Since the very first report of a heterodinuclear transition‐metal complex in 1960, a repertoire of methodologies for the targeted synthesis has been established. Besides the description of this progress, the focus of the present article is on the discussion of appropriate characterization methods. Typical questions concern the nature of the metal–metal bond as well as the elucidation of mechanistic details of reactions involving the polar metal–metal bonds present in heterodinuclear complexes. Several applications are detailed, in which heterodinuclear complexes either surpass the limitations of mononuclear complexes or even exhibit so far unknown reactivity. So‐called “early–late” complexes represent the most dominant branch in this context, while also “late–late” complexes show fruitful reactivity. Herein, the focus is on transition‐metal‐containing complexes, thus ignoring main‐group elements completely.

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Use of 155Gd, 151Eu, 166Er Mössbauer spectroscopy to characterize heterodinuclear Ln–Ln′ complexes

Cited by 4 publications

References 40 publications

Design of pure heterodinuclear lanthanoid cryptate complexes

Design of pure heterodinuclear lanthanoid cryptate complexes

Design of Pure Heterodinuclear Lanthanoid Cryptate Complexes

Heterodinuclear Transition‐Metal Complexes: Fundamentals, Synthesis, and Applications

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