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Beach, Stephanie A.; Guillet, Jesse L.; Lagueux, Sydney P.; Perfetti, Mauro; Livesay, Brooke N.; Shores, Matthew P.; Bacon, Jeffrey W.; Rheingold, Arnold L.; Arnold, Polly L.; Doerrer, Linda H. (, Chemical Communications)null (Ed.)The new PtVO(SOCR) 4 lantern complexes, 1 (R = CH 3 ) and 2 (R = Ph) behave as neutral O-donor ligands to Ln(OR) 3 with Ln = Ce, Nd. Four heterotrimetallic complexes with linear {LnOVPt} units were prepared: [Ln(ODtbp) 3 {PtVO(SOCR) 4 }] (Ln = Ce, 3Ce (R = CH 3 ), 4Ce (R = Ph); Nd, 3Nd (R = CH 3 ), 4Nd (R = Ph); ODtbp = 2,6-ditertbutylphenolate). Magnetic characterization confirms slow magnetic relaxation behaviour and suggests antiferromagnetic coupling across {Ln–OV} in all four complexes, with variations tunable as a function of Ln and R.more » « less
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Bunting, Philip C.; Atanasov, Mihail; Damgaard-Møller, Emil; Perfetti, Mauro; Crassee, Iris; Orlita, Milan; Overgaard, Jacob; van Slageren, Joris; Neese, Frank; Long, Jeffrey R. (, Science)null (Ed.)Orbital angular momentum is a prerequisite for magnetic anisotropy, although in transition metal complexes it is typically quenched by the ligand field. By reducing the basicity of the carbon donor atoms in a pair of alkyl ligands, we synthesized a cobalt(II) dialkyl complex, Co(C(SiMe 2 ONaph) 3 ) 2 (where Me is methyl and Naph is a naphthyl group), wherein the ligand field is sufficiently weak that interelectron repulsion and spin-orbit coupling play a dominant role in determining the electronic ground state. Assignment of a non-Aufbau (d x 2 –y 2 , d xy ) 3 (d xz , d yz ) 3 (d z 2 ) 1 electron configuration is supported by dc magnetic susceptibility data, experimental charge density maps, and ab initio calculations. Variable-field far-infrared spectroscopy and ac magnetic susceptibility measurements further reveal slow magnetic relaxation via a 450–wave number magnetic excited state.more » « less
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