English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Tools annual

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Tools monthly

Global: Zendy Plus monthly

Presents the access of premium content as premium feature

Premium Content

Global: Zendy Plus annual

Global: Zendy Free Plan

In recent work we have reported the synthesis and physical properties of near-linear Ln(II) (Ln = lanthanide) complexes utilizing the bulky bis(silylamide) {N(Si i Pr 3 ) 2 }. Herein, we synthesize trigonal-planar Ln(II) complexes by employing a smaller bis(silylamide), {N(Si t BuMe 2 ) 2 } (N**), to study the effects of this relatively rare Ln geometry/oxidation state combination on the magnetic and optical properties of complexes. We show that the charge-separated trigonal-planar Ln(II) complexes [K(2.2.2-cryptand)][Ln(N**) 3 ] (Ln = Sm (1), Eu (2), Tm (3), Yb (4)) can be prepared by the reaction of 1.5 equiv of [{K(N**)} 2 ] with LnI 2 THF 2 (Ln = Sm, Yb) or LnI 2 (Ln = Eu, Tm) and 1 equiv of 2.2.2-cryptand in Et 2 O. Complex 3 is the first structurally characterized trigonal-planar Tm(II) complex. In the absence of 2.2.2-cryptand, [K(DME) 3 ][Sm(N**) 3 ] (5) and [Ln(N**) 2 (μ-N**)K(toluene) 2 ] (Ln = Sm (6), Eu (7)) were isolated in the presence of DME (dimethoxyethane) or toluene, respectively. The 1:1 reaction of [{K(N**)} 2 ] with LnI 2 THF 2 (Ln = Sm, Yb) in THF gave the four-coordinate pseudo-tetrahedral Lewis base adducts [Ln(N**) 2 (THF) 2 ] (Ln = Sm (8), Yb (9)) and the cyclometalated complex [Yb(N**){N(Si t BuMe 2 )(Si t BuMeCH 2 )}(THF)] (10). Complexes 1-10 have been characterized as appropriate by single-crystal XRD, magnetic measurements, multinuclear NMR, EPR, and electronic spectroscopy, together with CASSCF-SO and DFT calculations. The physical properties of 1-4 are compared and contrasted with those of closely related near-linear Ln(II) bis(silylamide) complexes.

inorganic chemistry

Investigation into the Effects of a Trigonal-Planar Ligand Field on the Electronic Properties of Lanthanide(II) Tris(silylamide) Complexes (Ln = Sm, Eu, Tm, Yb)