Heterometallic [Ln(hfac)3Cu(acac)2] complexes with late 4f ions

Bellucci, Luca; Giordano, Luca; Carlotto, Silvia; Poneti, Giordano; Rancan, Marzio; Samaritani, Simona; Armelao, Lidia; Labella, Luca

doi:10.1016/j.ica.2023.121665

Cited by 2 publications

(1 citation statement)

References 97 publications

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“…The present finding clarifies that in anhydrous conditions, genuine heterometallic complexes [Ln(hfac) 3 Al(qNO) 3 ] can also be obtained for late transition metals. A similar result has been highlighted elsewhere for [Ln(hfac) 3 Cu(acac) 2 )] complexes [61]. For [Ln(hfac) 3 Al(qNO) 3 ] complexes, large early lanthanides significantly prefer the coordination number 9, with three donor atoms from three different qNO ligands lying on the same triangular face and bridging the two metal ions, while late transition metals possibly prefer the coordination number 8, with only two oxygen atoms bridging the two fragments.…”

Section: Nosupporting

confidence: 88%

Aluminium 8-Hydroxyquinolinate N-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes

Gallo,

Bellucci,

Carlotto

et al. 2024

Molecules

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A reaction in anhydrous toluene between the formally unsaturated fragment [Ln(hfac)3] (Ln3+ = Eu3+, Gd3+ and Er3+; Hhfac = hexafluoroacetylacetone) and [Al(qNO)3] (HqNO = 8-hydroxyquinoline N-oxide), here prepared for the first time from [Al(OtBu)3] and HqNO, affords the dinuclear heterometallic compounds [Ln(hfac)3Al(qNO)3] (Ln3+ = Eu3+, Gd3+ and Er3+) in high yields. The molecular structures of these new compounds revealed a dinuclear species with three phenolic oxygen atoms bridging the two metal atoms. While the europium and gadolinium complexes show the coordination number (CN) 9 for the lanthanide centre, in the complex featuring the smaller erbium ion, only two oxygens bridge the two metal atoms for a resulting CN of 8. The reaction of [Eu(hfac)3] with [Alq3] (Hq = 8-hydroxyquinoline) in the same conditions yields a heterometallic product of composition [Eu(hfac)3Alq3]. A recrystallization attempt from hot heptane in air produced single crystals of two different morphologies and compositions: [Eu2(hfac)6Al2q4(OH)2] and [Eu2(hfac)6(µ-Hq)2]. The latter compound can be directly prepared from [Eu(hfac)3] and Hq at room temperature. Quantum mechanical calculations confirm (i) the higher stability of [Eu(hfac)3Al(qNO)3] vs. the corresponding [Eu(hfac)3Alq3] and (ii) the preference of the Er complexes for the CN 8, justifying the different behaviour in terms of the Lewis acidity of the metal centre.

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Section: Nosupporting

confidence: 88%

Aluminium 8-Hydroxyquinolinate N-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes

Gallo,

Bellucci,

Carlotto

et al. 2024

Molecules

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Sandwich d/f Heterometallic Complexes [(Ln(hfac)3)2M(acac)3] (Ln = La, Pr, Sm, Dy and M = Co; Ln = La and M = Ru)

Grechi,

Carlotto,

Guelfi

et al. 2024

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Sandwich d/f heterometallic complexes [(Ln(hfac)3)2M(acac)3] (Ln = La, Pr, Sm, Dy and M = Co; Ln = La and M = Ru) were prepared in strictly anhydrous conditions reacting the formally unsaturated fragment [Ln(hfac)3] and [M(acac)3] in a 2-to-1 molar ratio. These heterometallic complexes are highly sensitive to moisture. Spectroscopic observation revealed that on hydrolysis, these compounds yield dinuclear heterometallic compounds [Ln(hfac)3M(acac)3], prepared here for comparison purposes only. Quantum mechanical calculations supported, on the one hand, the hypothesis on the geometrical arrangement obtained from ATR-IR and NMR spectra and, on the other hand, helped to rationalize the spontaneous hydrolysis reaction.

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Heterometallic [Ln(hfac)3Cu(acac)2] complexes with late 4f ions

Cited by 2 publications

References 97 publications

Aluminium 8-Hydroxyquinolinate N-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes

Aluminium 8-Hydroxyquinolinate N-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes

Sandwich d/f Heterometallic Complexes [(Ln(hfac)3)2M(acac)3] (Ln = La, Pr, Sm, Dy and M = Co; Ln = La and M = Ru)

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