TY - JOUR
T1 - A High-Performance Single-Molecule Magnet Utilizing Dianionic Aminoborolide Ligands
AU - Vanjak, James C
AU - Wilkins, Branford O
AU - Vieru, Veacheslav
AU - Bhuvanesh, Nattamai S
AU - Reibenspies, Joseph H
AU - Martin, Caleb D
AU - Chibotaru, Liviu F
AU - Nippe, Michael
N1 - Funding Information:
We are grateful to the Welch Foundation (M.N.: Grant A-1880; C.D.M.: Grant AA-1846) and the National Science Foundation (M.N.: Award CHE-1753014; C.D.M.: Award 1753025) for their generous support of this work.
Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022/10/5
Y1 - 2022/10/5
N2 - The first example of a homoleptic f-block borolide sandwich complex is presented and shown to be a high-performance single-molecule magnet (SMM). The bis(borolide) complex [K(2.2.2)][[1-(piperidino)-2,3,4,5-tetraphenylborolyl]2Dy] (1) features an unusual example of an anionic Ln3+ metallocene that supports short metal-ligand bonds and a high degree of linearity around the central Dy3+ ion, resulting in comparatively large barriers to magnetization reversal (Ueff = 1600 cm-1 for the most linear orientation) and, importantly, a high blocking temperature (TB, defined as T(τ100s)) of 66 K. These metrics put complex 1 among the very best performing SMMs reported to date and highlight the potential of dianionic borolide ligands to increase ligand field axiality, compared to monoanionic cyclic ligands, to ultimately maximize magnetic anisotropy in f-block-based SMMs.
AB - The first example of a homoleptic f-block borolide sandwich complex is presented and shown to be a high-performance single-molecule magnet (SMM). The bis(borolide) complex [K(2.2.2)][[1-(piperidino)-2,3,4,5-tetraphenylborolyl]2Dy] (1) features an unusual example of an anionic Ln3+ metallocene that supports short metal-ligand bonds and a high degree of linearity around the central Dy3+ ion, resulting in comparatively large barriers to magnetization reversal (Ueff = 1600 cm-1 for the most linear orientation) and, importantly, a high blocking temperature (TB, defined as T(τ100s)) of 66 K. These metrics put complex 1 among the very best performing SMMs reported to date and highlight the potential of dianionic borolide ligands to increase ligand field axiality, compared to monoanionic cyclic ligands, to ultimately maximize magnetic anisotropy in f-block-based SMMs.
U2 - 10.1021/jacs.2c06698
DO - 10.1021/jacs.2c06698
M3 - Article
C2 - 36162057
SN - 0002-7863
VL - 144
SP - 17743
EP - 17747
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 39
ER -