TY - JOUR
T1 - Magnetic properties of closo-carborane-based Co(II) single-ion complexes with O, S, Se, and Te bridging atoms
AU - Ona, Ofelia B.
AU - Peralta, Juan Ernesto
N1 - Funding Information:
This work has been financially supported by the grants PCB No. 2013-1401PCB, PIP No. 11220130100377CO, and 11220130100311CO ( Consejo Nacional de Investigaciones Científicas y Técnicas, Argentina ), UBACYT 20020150100157BA ( Universidad de Buenos Aires, Argentina ), PICT No. 201-0381 ( Agencia Nacional de Promoción Científica y Tecnológica, Argentina ). JMO-E acknowledges Spanish MICINN for financial support through project CTQ2018-094644-B-C22. JEP acknowledges support from the Office of Basic Energy Sciences, US Department of Energy , DE-SC0005027.
Publisher Copyright:
© 2019 Elsevier Ltd
PY - 2020
Y1 - 2020
N2 - We present a detailed computational analysis of a newly proposed family of Co(II) single-ion complexes with large magnetic anisotropy. Starting from previously proposed structures based on oxy- and thio-bridged 1,2-dicarba-closo-dodecaborane and 1,2-dicarba-closo-hexaborane, we explore the substitution of O and S bridging atoms by Se and Te atoms. Our calculations, based on CASSCF/NEVPT2 methods, show that these substitutions also lead to some large magnetic anisotropy complexes. Particularly, one of the proposed single-ion Se-bridged Co(II) chelated by 1,2-dicarba-closo-dodecaborane has a calculated anisotropy parameter D=-144 cm−1, and a single-ion Se-bridged Co(II) chelated by 1,2-dicarba-closo-hexaborane gives a calculated D=-133 cm−1. These large D values can be attributed in part to geometric distortion from Td symmetry at the Co(II) ion caused by the ligand structure, and in part to the electric effect of the Se atoms. Our results suggest that this strategy could be a feasible alternative to increase the magnetic anisotropy of single-ion transition metal complexes.
AB - We present a detailed computational analysis of a newly proposed family of Co(II) single-ion complexes with large magnetic anisotropy. Starting from previously proposed structures based on oxy- and thio-bridged 1,2-dicarba-closo-dodecaborane and 1,2-dicarba-closo-hexaborane, we explore the substitution of O and S bridging atoms by Se and Te atoms. Our calculations, based on CASSCF/NEVPT2 methods, show that these substitutions also lead to some large magnetic anisotropy complexes. Particularly, one of the proposed single-ion Se-bridged Co(II) chelated by 1,2-dicarba-closo-dodecaborane has a calculated anisotropy parameter D=-144 cm−1, and a single-ion Se-bridged Co(II) chelated by 1,2-dicarba-closo-hexaborane gives a calculated D=-133 cm−1. These large D values can be attributed in part to geometric distortion from Td symmetry at the Co(II) ion caused by the ligand structure, and in part to the electric effect of the Se atoms. Our results suggest that this strategy could be a feasible alternative to increase the magnetic anisotropy of single-ion transition metal complexes.
M3 - Article
SN - 0277-5387
VL - 176
JO - Polyhedron
JF - Polyhedron
ER -