Projects per year
Abstract
The synthesis of the bulky divalent (polyphenylcyclopentadienyl)lanthanoid sandwich complexes [Ln(C5Ph5)2] (Ln = Sm, Eu) and [Ln(C5Ph4H)2(solv)] (Ln = Sm, solv = thf; Ln = Eu, solv = dme)], from redox-transmetalation/protolysis (RTP) reactions, has been achieved. An analogous reaction with Yb afforded the solvent-separated ion pair [Yb(dme)4][C5Ph4H]2. In addition, rare divalent samarium halide complexes [Sm(C5Ph5)(μ-Br)(thf)2]2 and [Sm(C5Ph4H)I(thf)3], were also prepared, either by RTP or ligand rearrangement. X-ray studies showed that the [Ln(C5Ph5)2] complexes adopt highly symmetrical sandwich structures, whereas the [Ln(C5Ph4H)2(solv)] complexes have open sandwich structures. The unexpected, but limited, solubility of the [Ln(C5Ph5)2] complexes allowed for variable-temperature NMR spectra of [Sm(C5Ph5)2] to be obtained. Detailed 1D and 2D NMR studies were conducted on [Sm(C5Ph4H)2(thf)] to ascertain its structure in donor and nondonor solvents. During the course of these studies, the mixed tetraarylcyclopentadienyl sandwich complex [Sm{C5(2,5-Ph)2(3,4-p-tol2)H}2(thf)] was also prepared in order to fully assign the spectrum of [Sm(C5Ph4H)2(thf)]. The europium sandwich complexes [Eu(C5Ph5)2] and [Eu(C5Ph4H)2(dme)] exhibit remarkable luminescence properties with high quantum yields (45% and 41%, respectively) coupled with long emission lifetimes (approximately 800 and 1300 ns, respectively) in toluene
Original language | English |
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Pages (from-to) | 5624-5636 |
Number of pages | 13 |
Journal | Organometallics |
Volume | 34 |
Issue number | 23 |
DOIs | |
Publication status | Published - 2015 |
Projects
- 3 Finished
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Reactive metal-organics embracing the rare earth and alkaline earth metals
Junk, P. C., Deacon, G., Jaroschik, F. & Anwander, R.
Australian Research Council (ARC)
1/01/16 → 31/12/18
Project: Research
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New Generation Functional Materials for 21st Century Applications - Exploiting the Properties of Naphthalene Diimides
Langford, S., Bell, T., Ayyappanpillai, A., Prodi, L. & Thang, S.
Australian Research Council (ARC), Monash University
3/01/13 → 4/08/16
Project: Research
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Advancing the chemistry of topical Rare Earth metals
Junk, P. C. & Mashima, K.
Australian Research Council (ARC), Monash University
3/01/13 → 31/12/15
Project: Research