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Spectroscopic and Theoretical Investigation of High-Spin Square-Planar and Trigonal Fe(II) Complexes Supported by Fluorinated Alkoxides

https://doi.org/10.1021/acs.inorgchem.3c03236

Toubiana, Léa A; Valaydon-Pillay, Adam; Elinburg, Jessica K; Bacon, Jeffrey W; Ozarowski, Andrew; Doerrer, Linda H; Stoian, Sebastian A (February 2024, Inorganic Chemistry)

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Heterotrimetallic {LnOVPt} complexes with antiferromagnetic Ln–V coupling and magnetic memory

https://doi.org/10.1039/D0CC04334F

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. (September 2020, Chemical Communications)
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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–OV} in all four complexes, with variations tunable as a function of Ln and R.
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Square-planar Co( iii ) in {O ₄ } coordination: large ZFS and reactivity with ROS

https://doi.org/10.1039/c8cc04464c

Steele, Jennifer L.; Tahsini, Laleh; Sun, Chen; Elinburg, Jessica K.; Kotyk, Christopher M.; McNeely, James; Stoian, Sebastian A.; Dragulescu-Andrasi, Alina; Ozarowski, Andrew; Ozerov, M.; et al (October 2018, Chemical Communications)

Oxidation of distorted square-planar perfluoropinacolate Co compound [Co II (pin F ) 2 ] 2− , 1 , to [Co III (pin F ) 2 ] 1− , 2 , is reported. Rigidly square-planar 2 has an intermediate-spin, S = 1, ground state and very large zero-field splitting (ZFS) with D = 67.2 cm −1 ; | E | = 18.0 cm −1 , ( E / D = 0.27), g ⊥ = 2.10, g ‖ = 2.25 and χ TIP = 1950 × 10 −6 cm 3 mol −1 . This Co( iii ) species, 2 , reacts with ROS to oxidise two (pin F ) 2− ligands to form tetrahedral [Co II (Hpfa) 4 ] 2− , 3 .
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