2021
DOI: 10.1002/chem.202101599
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Size‐Controlled Hapticity Switching in [Ln(C9H9)(C8H8)] Sandwiches

Abstract: Sandwich complexes of lanthanides have recently attracted a considerable amount of interest due to their applications as Single Molecule Magnet (SMM). Herein, a comprehensive series of heteroleptic lanthanide sandwich complexes ligated by the cyclononatetraenyl (Cnt) and the cyclooctatetraenyl (Cot) ligand [Ln(Cot)(Cnt)] (Ln=Tb, Dy, Er, Ho, Yb, and Lu) is reported. The coordination behavior of the Cnt ligand has been investigated along the series and shows different coordination patterns in the solid‐state dep… Show more

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Cited by 12 publications
(11 citation statements)
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“…Upon addition of THF to solid samples of these [(CNT)Ln(η 8 ‐COT)] (Ln=La, Ce, Nd, Tb, Er) complexes, an immediate colour change of the insoluble materials can be observed (La: orange to colourless; Ce: green to light‐yellow (at −10 °C) or green to red (at room temperature, see below); Nd: yellow to green; Tb: orange to colourless; Er: orange to light‐pink). A colour change is often indicative for the transformation of the chemical environment of lanthanide ions; in the present scenario, the colour change is very likely due to THF coordination [10a,c] …”
Section: Resultsmentioning
confidence: 73%
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“…Upon addition of THF to solid samples of these [(CNT)Ln(η 8 ‐COT)] (Ln=La, Ce, Nd, Tb, Er) complexes, an immediate colour change of the insoluble materials can be observed (La: orange to colourless; Ce: green to light‐yellow (at −10 °C) or green to red (at room temperature, see below); Nd: yellow to green; Tb: orange to colourless; Er: orange to light‐pink). A colour change is often indicative for the transformation of the chemical environment of lanthanide ions; in the present scenario, the colour change is very likely due to THF coordination [10a,c] …”
Section: Resultsmentioning
confidence: 73%
“…Lifetimes of the excited states of 4 were determined to be ≈95 μs at room temperature and ≈570 μs at 77 K (Table S15), being in the range of literature values [18] . Although PLE spectra differ in energetic position and band shape, which is assigned to the different ligands, emission spectra of 4 and [Tb(COT)I(thf) 2 ] [10c] look very alike, confirming the emission taking place from the lanthanide centre regardless of the differences in the coordination environment (see Figure S19).…”
Section: Resultsmentioning
confidence: 91%
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“…183 The use of heteroleptic ligands for the formation of neutral -sandwich complexes was also investigated and led to good SMMs properties, 184,185 particularly with the large monoanionic Cnt ligand. 186,187 The Cot-Er pair is highly relevant as an excellent example of the perfect adequation between the metal and the ligand coordination for maximal anisotropy: this is referred to as ligand-metal pair anisotropy. 188,189 The concept has been extended to divalent thulium, an ion with prolateshaped density.…”
Section: Single-ion Magnet Designmentioning
confidence: 99%