Building-up host-guest helicate motifs and chains: a magneto-structural study of new field-induced cobalt-based single-ion magnets

In this work, we present the synthetic pathway, a refined structural description, complete solid-state characterization and the magnetic properties of four new cobalt( ii ) compounds of formulas [Co(H 2 O) 6 ][Co 2 (H 2 mpba) 3 ]·2H 2 O·0.5dmso ( 1 ), [Co(H 2 O) 6 ][Co 2 (H 2 mpba) 3 ]·3H 2 O·0.5dps...

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Published inDalton transactions : an international journal of inorganic chemistry Vol. 5; no. 31; pp. 177 - 1728
Main Authors de Campos, Nathália R, Simosono, Cintia A, Landre Rosa, Iara M, da Silva, Rafaela M. R, Doriguetto, Antônio C, do Pim, Walace D, Gomes Simões, Tatiana R, Valdo, Ana Karoline S. M, Martins, Felipe T, Sarmiento, Charlie V, Nunes, Wallace C, Guedes, Guilherme P, Pedroso, Emerson F, Pereira, Cynthia L. M, Stumpf, Humberto O, Lloret, Francesc, Julve, Miguel, Marinho, Maria Vanda
Format Journal Article
LanguageEnglish
Published Cambridge Royal Society of Chemistry 21.08.2021
Subjects
Chains
Cobalt compounds
Crystallization
Crystallography
Diffraction patterns
Diffusion rate
Hydrogen bonds
Magnetic measurement
Magnetic permeability
Magnetic properties
Magnets
Room temperature
Spin-orbit interactions
Structural analysis
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Abstract In this work, we present the synthetic pathway, a refined structural description, complete solid-state characterization and the magnetic properties of four new cobalt( ii ) compounds of formulas [Co(H 2 O) 6 ][Co 2 (H 2 mpba) 3 ]·2H 2 O·0.5dmso ( 1 ), [Co(H 2 O) 6 ][Co 2 (H 2 mpba) 3 ]·3H 2 O·0.5dpss ( 2 ), [Co 2 (H 2 mpba) 2 (H 2 O) 4 ] n ·4 n H 2 O ( 3 ), and [Co 2 (H 2 mpba) 2 (CH 3 OH) 2 (H 2 O) 2 ] n ·0.5 n H 2 O·2 n dpss ( 4 ) [dpss = 2,2′-dipyridyldisulfide and H 4 mpba = 1,3-phenylenebis(oxamic) acid], where 2 and 4 were obtained from [Co(dpss)Cl 2 ] ( Pre-I ) as the source of cobalt( ii ). All four compounds are air-stable and were prepared under ambient conditions. 1 and 2 were obtained from a slow diffusion method [cobalt( ii ) : H 2 mpba 2− molar ratio used 1 : 1] and their structures are made up of [Co 2 (H 2 mpba) 3 ] 2− anionic helicate units and [Co(H 2 O) 6 ] 2+ cations, exhibiting supramolecular three-dimensional structures. Interestingly, a supramolecular honeycomb network between the helicate units interacting with each other through R 2 2 (10) type hydrogen bonds occurs in 2 hosting one co-crystallized dpss molecule. On the other hand, for the first time, linear ( 3 ) and zigzag ( 4 ) cobalt( ii ) chains were isolated by slow evaporation of stirred solutions of mixed solvents with cobalt( ii ) : H 2 mpba 2− in 1 : 2 molar ratio at room temperature. Magnetic measurements of Pre-I revealed a quasi magnetically isolated S = 3/2 spin state with a significant second-order spin-orbit contribution as expected for tetrahedrally coordinated cobalt( ii ) ions. The analysis of the variable temperature static (dc) magnetic susceptibility data through first- ( 1 and 3 ) and second-order spin-orbit coupling models ( 2 and 4 ) reveals the presence of magnetically non-interacting high-spin cobalt( ii ) ions with easy-axis ( 1 and 4 )/easy-plane magnetic anisotropies ( 2 and 4 ) with low rhombic distortions. Dynamic (ac) magnetic measurements for Pre-I and 1-4 below 8.0 K show that they are examples of field-induced Single-Ion Magnets (SIMs). The slow diffusion method affords host-guest systems ( 1 and 2 ), while the stirring method results in chains ( 3 and 4 ) that behave as field-induced cobalt-based Single-Ion Magnets (SIMs).
AbstractList In this work, we present the synthetic pathway, a refined structural description, complete solid-state characterization and the magnetic properties of four new cobalt(ii) compounds of formulas [Co(H2O)6][Co2(H2mpba)3]·2H2O·0.5dmso (1), [Co(H2O)6][Co2(H2mpba)3]·3H2O·0.5dpss (2), [Co2(H2mpba)2(H2O)4]n·4nH2O (3), and [Co2(H2mpba)2(CH3OH)2(H2O)2]n·0.5nH2O·2ndpss (4) [dpss = 2,2′-dipyridyldisulfide and H4mpba = 1,3-phenylenebis(oxamic) acid], where 2 and 4 were obtained from [Co(dpss)Cl2] (Pre-I) as the source of cobalt(ii). All four compounds are air-stable and were prepared under ambient conditions. 1 and 2 were obtained from a slow diffusion method [cobalt(ii) : H2mpba2− molar ratio used 1 : 1] and their structures are made up of [Co2(H2mpba)3]2− anionic helicate units and [Co(H2O)6]2+ cations, exhibiting supramolecular three-dimensional structures. Interestingly, a supramolecular honeycomb network between the helicate units interacting with each other through R22(10) type hydrogen bonds occurs in 2 hosting one co-crystallized dpss molecule. On the other hand, for the first time, linear (3) and zigzag (4) cobalt(ii) chains were isolated by slow evaporation of stirred solutions of mixed solvents with cobalt(ii) : H2mpba2− in 1 : 2 molar ratio at room temperature. Magnetic measurements of Pre-I revealed a quasi magnetically isolated S = 3/2 spin state with a significant second-order spin–orbit contribution as expected for tetrahedrally coordinated cobalt(ii) ions. The analysis of the variable temperature static (dc) magnetic susceptibility data through first- (1 and 3) and second-order spin–orbit coupling models (2 and 4) reveals the presence of magnetically non-interacting high-spin cobalt(ii) ions with easy-axis (1 and 4)/easy-plane magnetic anisotropies (2 and 4) with low rhombic distortions. Dynamic (ac) magnetic measurements for Pre-I and 1–4 below 8.0 K show that they are examples of field-induced Single-Ion Magnets (SIMs).
In this work, we present the synthetic pathway, a refined structural description, complete solid-state characterization and the magnetic properties of four new cobalt( ii ) compounds of formulas [Co(H 2 O) 6 ][Co 2 (H 2 mpba) 3 ]·2H 2 O·0.5dmso ( 1 ), [Co(H 2 O) 6 ][Co 2 (H 2 mpba) 3 ]·3H 2 O·0.5dpss ( 2 ), [Co 2 (H 2 mpba) 2 (H 2 O) 4 ] n ·4 n H 2 O ( 3 ), and [Co 2 (H 2 mpba) 2 (CH 3 OH) 2 (H 2 O) 2 ] n ·0.5 n H 2 O·2 n dpss ( 4 ) [dpss = 2,2′-dipyridyldisulfide and H 4 mpba = 1,3-phenylenebis(oxamic) acid], where 2 and 4 were obtained from [Co(dpss)Cl 2 ] ( Pre-I ) as the source of cobalt( ii ). All four compounds are air-stable and were prepared under ambient conditions. 1 and 2 were obtained from a slow diffusion method [cobalt( ii ) : H 2 mpba 2− molar ratio used 1 : 1] and their structures are made up of [Co 2 (H 2 mpba) 3 ] 2− anionic helicate units and [Co(H 2 O) 6 ] 2+ cations, exhibiting supramolecular three-dimensional structures. Interestingly, a supramolecular honeycomb network between the helicate units interacting with each other through R 2 2 (10) type hydrogen bonds occurs in 2 hosting one co-crystallized dpss molecule. On the other hand, for the first time, linear ( 3 ) and zigzag ( 4 ) cobalt( ii ) chains were isolated by slow evaporation of stirred solutions of mixed solvents with cobalt( ii ) : H 2 mpba 2− in 1 : 2 molar ratio at room temperature. Magnetic measurements of Pre-I revealed a quasi magnetically isolated S = 3/2 spin state with a significant second-order spin-orbit contribution as expected for tetrahedrally coordinated cobalt( ii ) ions. The analysis of the variable temperature static (dc) magnetic susceptibility data through first- ( 1 and 3 ) and second-order spin-orbit coupling models ( 2 and 4 ) reveals the presence of magnetically non-interacting high-spin cobalt( ii ) ions with easy-axis ( 1 and 4 )/easy-plane magnetic anisotropies ( 2 and 4 ) with low rhombic distortions. Dynamic (ac) magnetic measurements for Pre-I and 1-4 below 8.0 K show that they are examples of field-induced Single-Ion Magnets (SIMs). The slow diffusion method affords host-guest systems ( 1 and 2 ), while the stirring method results in chains ( 3 and 4 ) that behave as field-induced cobalt-based Single-Ion Magnets (SIMs).
In this work, we present the synthetic pathway, a refined structural description, complete solid-state characterization and the magnetic properties of four new cobalt( ii ) compounds of formulas [Co(H 2 O) 6 ][Co 2 (H 2 mpba) 3 ]·2H 2 O·0.5dmso ( 1 ), [Co(H 2 O) 6 ][Co 2 (H 2 mpba) 3 ]·3H 2 O·0.5dpss ( 2 ), [Co 2 (H 2 mpba) 2 (H 2 O) 4 ] n ·4 n H 2 O ( 3 ), and [Co 2 (H 2 mpba) 2 (CH 3 OH) 2 (H 2 O) 2 ] n ·0.5 n H 2 O·2 n dpss ( 4 ) [dpss = 2,2′-dipyridyldisulfide and H 4 mpba = 1,3-phenylenebis(oxamic) acid], where 2 and 4 were obtained from [Co(dpss)Cl 2 ] ( Pre-I ) as the source of cobalt( ii ). All four compounds are air-stable and were prepared under ambient conditions. 1 and 2 were obtained from a slow diffusion method [cobalt( ii ) : H 2 mpba 2− molar ratio used 1 : 1] and their structures are made up of [Co 2 (H 2 mpba) 3 ] 2− anionic helicate units and [Co(H 2 O) 6 ] 2+ cations, exhibiting supramolecular three-dimensional structures. Interestingly, a supramolecular honeycomb network between the helicate units interacting with each other through R 2 2 (10) type hydrogen bonds occurs in 2 hosting one co-crystallized dpss molecule. On the other hand, for the first time, linear ( 3 ) and zigzag ( 4 ) cobalt( ii ) chains were isolated by slow evaporation of stirred solutions of mixed solvents with cobalt( ii ) : H 2 mpba 2− in 1 : 2 molar ratio at room temperature. Magnetic measurements of Pre-I revealed a quasi magnetically isolated S = 3/2 spin state with a significant second-order spin–orbit contribution as expected for tetrahedrally coordinated cobalt( ii ) ions. The analysis of the variable temperature static (dc) magnetic susceptibility data through first- ( 1 and 3 ) and second-order spin–orbit coupling models ( 2 and 4 ) reveals the presence of magnetically non-interacting high-spin cobalt( ii ) ions with easy-axis ( 1 and 4 )/easy-plane magnetic anisotropies ( 2 and 4 ) with low rhombic distortions. Dynamic (ac) magnetic measurements for Pre-I and 1–4 below 8.0 K show that they are examples of field-induced Single-Ion Magnets (SIMs).
Author Sarmiento, Charlie V
Stumpf, Humberto O
Gomes Simões, Tatiana R
Landre Rosa, Iara M
Pedroso, Emerson F
Julve, Miguel
Martins, Felipe T
de Campos, Nathália R
Lloret, Francesc
Valdo, Ana Karoline S. M
Simosono, Cintia A
Nunes, Wallace C
Doriguetto, Antônio C
da Silva, Rafaela M. R
Pereira, Cynthia L. M
do Pim, Walace D
Guedes, Guilherme P
Marinho, Maria Vanda
AuthorAffiliation Departament de Química Inorgànica/Instituto de Ciencia Molecular (ICMol)
Universidade Federal Fluminense
Campus Santa Clara
Universidade Federal do Paraná
Instituto de Física
Departamento de Química
Instituto de Química
Universitat de València
Universidade Federal de Minas Gerais
Centro Federal de Educação Tecnológica de Minas Gerais
Universidade Federal de Goiás
Departamento de Química-ICEx
Universidade Federal de Alfenas
AuthorAffiliation_xml – name: Universidade Federal de Goiás
– name: Universidade Federal de Alfenas
– name: Instituto de Física
– name: Universidade Federal Fluminense
– name: Campus Santa Clara
– name: Universidade Federal de Minas Gerais
– name: Departament de Química Inorgànica/Instituto de Ciencia Molecular (ICMol)
– name: Departamento de Química-ICEx
– name: Centro Federal de Educação Tecnológica de Minas Gerais
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  day: 21
PublicationDecade 2020
PublicationPlace Cambridge
PublicationPlace_xml – name: Cambridge
PublicationTitle Dalton transactions : an international journal of inorganic chemistry
PublicationYear 2021
Publisher Royal Society of Chemistry
Publisher_xml – name: Royal Society of Chemistry
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Snippet In this work, we present the synthetic pathway, a refined structural description, complete solid-state characterization and the magnetic properties of four new...
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StartPage 177
SubjectTerms Chains
Cobalt compounds
Crystallization
Crystallography
Diffraction patterns
Diffusion rate
Hydrogen bonds
Magnetic measurement
Magnetic permeability
Magnetic properties
Magnets
Room temperature
Spin-orbit interactions
Structural analysis
Title Building-up host-guest helicate motifs and chains: a magneto-structural study of new field-induced cobalt-based single-ion magnets
URI https://www.proquest.com/docview/2559621577
https://search.proquest.com/docview/2555349145
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