Magnetic properties of closo-carborane-based Co(II) single-ion complexes with O, S, Se, and Te bridging atoms

Ofelia B. Oña; Diego R. Alcoba; Gustavo E. Massaccesi; Alicia Torre; Luis Lain; Juan I. Melo; Josep M. Oliva-Enrich; Juan E. Peralta

doi:10.1016/j.poly.2019.114257

Magnetic properties of closo-carborane-based Co(II) single-ion complexes with O, S, Se, and Te bridging atoms

Ofelia B. Oña, Diego R. Alcoba, Gustavo E. Massaccesi, Alicia Torre, Luis Lain, Juan I. Melo, Josep M. Oliva-Enrich, Juan E. Peralta

Physics

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

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 T_d 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.

Original language	English
Article number	114257
Journal	Polyhedron
Volume	176
DOIs	https://doi.org/10.1016/j.poly.2019.114257
State	Published - Jan 15 2020

Keywords

Carboranes
Co(II) complexes
Magnetic anisotropy
Spin relaxation

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10.1016/j.poly.2019.114257

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@article{f5a0693eb1d348f7aa3dbf1e31676f6e,

title = "Magnetic properties of closo-carborane-based Co(II) single-ion complexes with O, S, Se, and Te bridging atoms",

abstract = "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.",

keywords = "Carboranes, Co(II) complexes, Magnetic anisotropy, Spin relaxation",

author = "O{\~n}a, {Ofelia B.} and Alcoba, {Diego R.} and Massaccesi, {Gustavo E.} and Alicia Torre and Luis Lain and Melo, {Juan I.} and Oliva-Enrich, {Josep M.} and Peralta, {Juan E.}",

note = "Funding Information: This work has been financially supported by the grants PCB No. 2013-1401PCB, PIP No. 11220130100377CO, and 11220130100311CO ( Consejo Nacional de Investigaciones Cient{\'i}ficas y T{\'e}cnicas, Argentina ), UBACYT 20020150100157BA ( Universidad de Buenos Aires, Argentina ), PICT No. 201-0381 ( Agencia Nacional de Promoci{\'o}n Cient{\'i}fica y Tecnol{\'o}gica, 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: {\textcopyright} 2019 Elsevier Ltd",

year = "2020",

month = jan,

day = "15",

doi = "10.1016/j.poly.2019.114257",

language = "English",

volume = "176",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Polyhedron",

}

TY - JOUR

T1 - Magnetic properties of closo-carborane-based Co(II) single-ion complexes with O, S, Se, and Te bridging atoms

AU - Oña, Ofelia B.

AU - Alcoba, Diego R.

AU - Massaccesi, Gustavo E.

AU - Torre, Alicia

AU - Lain, Luis

AU - Melo, Juan I.

AU - Oliva-Enrich, Josep M.

AU - Peralta, Juan E.

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 - 2020/1/15

Y1 - 2020/1/15

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.

KW - Carboranes

KW - Co(II) complexes

KW - Magnetic anisotropy

KW - Spin relaxation

UR - http://www.scopus.com/inward/record.url?scp=85076625109&partnerID=8YFLogxK

U2 - 10.1016/j.poly.2019.114257

DO - 10.1016/j.poly.2019.114257

M3 - Article

AN - SCOPUS:85076625109

SN - 0277-5387

VL - 176

JO - Polyhedron

JF - Polyhedron

M1 - 114257

ER -

Magnetic properties of closo-carborane-based Co(II) single-ion complexes with O, S, Se, and Te bridging atoms

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Keywords

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