Divalent ansa-Octaphenyllanthanocenes: Synthesis, Structures, and EuII Luminescence

Shephard, Angus C.G., Delon, Aymeric, Chevreux, Sylviane, Martinez, Agathe, Guo, Zhifang, Deacon, Glen B., Lemercier, Gilles, McClenaghan, Nathan, Jonusauskas, Gediminas, Junk, Peter C., and Jaroschik, Florian (2024) Divalent ansa-Octaphenyllanthanocenes: Synthesis, Structures, and EuII Luminescence. Inorganic Chemistry. (In Press)

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Reductive dimerization of fulvenes using low-valent metal precursors is a straightforward one-step approach to access ethylene-bridged metallocenes. This process has so far mainly been employed with fulvenes carrying one or two substituents in the exocyclic position. In this work, a new synthesis of the unsubstituted exocyclic 1,2,3,4-tetraphenylfulvene (1), its full structural characterization by NMR spectroscopy and single-crystal X-ray diffraction, as well as some photophysical properties and its first use in reductive dimerization are described. This fulvene reacted with different lanthanoid metals in thf to provide the divalent ansa-octaphenylmetallocenes [Ln(C5Ph4CH2)2(thf)n] (Ln = Sm, n = 2 (2); Ln = Eu, n = 2 (3); and Ln = Yb, n = 1 (4)). These complexes were characterized by X-ray diffraction, laser desorption/ionization time of flight mass spectrometry, and, in the case of Sm and Yb, multinuclear NMR spectroscopy, showing the influence of the ansa-bridge on solution and solid-state structures compared to previously reported unbridged metallocenes. Furthermore, the luminescence properties of the Eu ansa complex 3 were studied in solution and the solid state, revealing significant differences with the known octa- and deca-phenyleuropocenes, [Eu(C5Ph4H)2(dme)] and [Eu(C5Ph5)2].

Item ID: 79550
Item Type: Article (Research - C1)
ISSN: 1520-510X
Copyright Information: © 2023 American Chemical Society
Funders: Australian Research Council (ARC)
Projects and Grants: ARC (DP190100798), ARC (DP230100112)
Date Deposited: 23 Jan 2024 04:38
FoR Codes: 34 CHEMICAL SCIENCES > 3402 Inorganic chemistry > 340203 F-block chemistry @ 100%
SEO Codes: 28 EXPANDING KNOWLEDGE > 2801 Expanding knowledge > 280105 Expanding knowledge in the chemical sciences @ 100%
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