Effects of weak intramolecular interactions and distortions from trigonal prismatic coordination on the magnetic properties of zero-field Co() single-ion magnets
The mononuclear cobalt( ii ) complexes [Co(L N8 )](BPh 4 ) 2 ·C 4 H 10 O ( 1-BPh 4 ) and [Co(L N8 )](NO 3 ) 2 ·CH 3 CN ( 2-NO 3 ) (L N8 = 1,4,7,10-tetrakis(2-pyridinemethyl)-1,4,7,10-tetraaza-cyclododecane) have been synthesized and fully characterized. They differ well beyond a formal replacement o...
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| Veröffentlicht in: | Inorganic chemistry frontiers 2024-04, Vol.11 (9), p.2648-266 |
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| creator | Zhang, Ben Zhou, Yang Huang, Hao-Yi Zhang, Xiao-Le Xiang, Yi Shi, Yanbo Zhang, Chennan Yuan, Aihua Cai, Xingwei Chen, Lei Zhang, Yi-Quan Hu, Zhao-Bo |
| description | The mononuclear cobalt(
ii
) complexes [Co(L
N8
)](BPh
4
)
2
·C
4
H
10
O (
1-BPh
4
) and [Co(L
N8
)](NO
3
)
2
·CH
3
CN (
2-NO
3
) (L
N8
= 1,4,7,10-tetrakis(2-pyridinemethyl)-1,4,7,10-tetraaza-cyclododecane) have been synthesized and fully characterized. They differ well beyond a formal replacement of the counter anions, with their Co(
ii
) centers in significantly different coordination geometries. In
1-BPh
4
, the Co(
ii
) ion is not only coordinated by six N atoms from the L
N8
ligand but also associated with the two remaining N atoms of L
N8
via
weak interactions. In contrast, the Co(
ii
) ion in
2-NO
3
is only six-coordinated in a distorted trigonal prismatic geometry. Magnetic anisotropy and slow magnetic dynamics are drastically affected by these different environments around Co(
ii
). The combination of dc magnetic data, high-frequency and -field electron paramagnetic resonance (HFEPR) and theoretical calculations unambiguously reveals large negative zero-field split (ZFS) parameters
D
for both complexes and a large difference between the
D
values. Both
1-BPh
4
and
2-NO
3
show slow magnetic relaxation at zero field. Magnetic dilution experiments reveal effective energy barriers of 54(4) cm
−1
for
1-BPh
4
@Zn
and 95(5) cm
−1
for
2-NO
3
@Zn
and confirm that the slow magnetic relaxation for both complexes originates from single molecule behaviour.
Ab initio
computational studies explain their electronic structures and the origin of the large negative magnetic anisotropy; they support the corresponding experimental observations. Further magneto-structural analyses reveal that different distortions from the ideal trigonal prismatic geometry exert drastic effects on
D
values and slow relaxation, and that the additional weak intramolecular interactions between Co and N reduce the axial anisotropy.
The change of counter anions significantly affects the environment around Co(
ii
) ions, leading to two zero-field single-ion magnets possessing different uniaxial anisotropies and dynamic magnetic properties. |
| doi_str_mv | 10.1039/d3qi02507a |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1039_D3QI02507A</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>3048329543</sourcerecordid><originalsourceid>FETCH-LOGICAL-c281t-6fd76968e7b9def394d68fc870e0cd8d2649da82ab2d22346db546eccaffafc13</originalsourceid><addsrcrecordid>eNpNkd9LwzAQx4MoOOZefBcCvqhQzY82ax_HnDoYiKDPJUsuM7NttiRD9L_xP7VdRYWDu-M-94svQqeUXFPCixvNt5awjIzlARowkrGEZhk__Bcfo1EIa0IIpSmhggzQ18wYUDFgZ_A7yDdsm-hl7SpQu0r6LgUvVbSuCVg2GmsbovN9bryrcfR25RpZ4Y23oZbRKqyc89o2sqNwa_EVcC1XDXTFjXcbaAfAfucneJcYC5XGU3dxiYNtVhUkXWPfEU7QkZFVgNGPH6KXu9nz9CFZPN7Pp5NFolhOYyKMHotC5DBeFhoML1ItcqPyMQGidK6ZSAstcyaXTDPGU6GXWSpAKWmMNIryITrv57YHbncQYrl2O98-FkpO0pyzIkt5S131lPIuBA-mbN-upf8oKSk7Fcpb_jTfqzBp4bMe9kH9cn8q8W918Iim</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>3048329543</pqid></control><display><type>article</type><title>Effects of weak intramolecular interactions and distortions from trigonal prismatic coordination on the magnetic properties of zero-field Co() single-ion magnets</title><source>Royal Society Of Chemistry Journals 2008-</source><creator>Zhang, Ben ; Zhou, Yang ; Huang, Hao-Yi ; Zhang, Xiao-Le ; Xiang, Yi ; Shi, Yanbo ; Zhang, Chennan ; Yuan, Aihua ; Cai, Xingwei ; Chen, Lei ; Zhang, Yi-Quan ; Hu, Zhao-Bo</creator><creatorcontrib>Zhang, Ben ; Zhou, Yang ; Huang, Hao-Yi ; Zhang, Xiao-Le ; Xiang, Yi ; Shi, Yanbo ; Zhang, Chennan ; Yuan, Aihua ; Cai, Xingwei ; Chen, Lei ; Zhang, Yi-Quan ; Hu, Zhao-Bo</creatorcontrib><description>The mononuclear cobalt(
ii
) complexes [Co(L
N8
)](BPh
4
)
2
·C
4
H
10
O (
1-BPh
4
) and [Co(L
N8
)](NO
3
)
2
·CH
3
CN (
2-NO
3
) (L
N8
= 1,4,7,10-tetrakis(2-pyridinemethyl)-1,4,7,10-tetraaza-cyclododecane) have been synthesized and fully characterized. They differ well beyond a formal replacement of the counter anions, with their Co(
ii
) centers in significantly different coordination geometries. In
1-BPh
4
, the Co(
ii
) ion is not only coordinated by six N atoms from the L
N8
ligand but also associated with the two remaining N atoms of L
N8
via
weak interactions. In contrast, the Co(
ii
) ion in
2-NO
3
is only six-coordinated in a distorted trigonal prismatic geometry. Magnetic anisotropy and slow magnetic dynamics are drastically affected by these different environments around Co(
ii
). The combination of dc magnetic data, high-frequency and -field electron paramagnetic resonance (HFEPR) and theoretical calculations unambiguously reveals large negative zero-field split (ZFS) parameters
D
for both complexes and a large difference between the
D
values. Both
1-BPh
4
and
2-NO
3
show slow magnetic relaxation at zero field. Magnetic dilution experiments reveal effective energy barriers of 54(4) cm
−1
for
1-BPh
4
@Zn
and 95(5) cm
−1
for
2-NO
3
@Zn
and confirm that the slow magnetic relaxation for both complexes originates from single molecule behaviour.
Ab initio
computational studies explain their electronic structures and the origin of the large negative magnetic anisotropy; they support the corresponding experimental observations. Further magneto-structural analyses reveal that different distortions from the ideal trigonal prismatic geometry exert drastic effects on
D
values and slow relaxation, and that the additional weak intramolecular interactions between Co and N reduce the axial anisotropy.
The change of counter anions significantly affects the environment around Co(
ii
) ions, leading to two zero-field single-ion magnets possessing different uniaxial anisotropies and dynamic magnetic properties.</description><identifier>ISSN: 2052-1553</identifier><identifier>ISSN: 2052-1545</identifier><identifier>EISSN: 2052-1553</identifier><identifier>DOI: 10.1039/d3qi02507a</identifier><language>eng</language><publisher>London: Royal Society of Chemistry</publisher><subject>Anisotropy ; Cobalt compounds ; Coordination ; Dilution ; Electron paramagnetic resonance ; Magnetic anisotropy ; Magnetic induction ; Magnetic properties ; Magnetic relaxation ; Magnets ; Mathematical analysis</subject><ispartof>Inorganic chemistry frontiers, 2024-04, Vol.11 (9), p.2648-266</ispartof><rights>Copyright Royal Society of Chemistry 2024</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c281t-6fd76968e7b9def394d68fc870e0cd8d2649da82ab2d22346db546eccaffafc13</citedby><cites>FETCH-LOGICAL-c281t-6fd76968e7b9def394d68fc870e0cd8d2649da82ab2d22346db546eccaffafc13</cites><orcidid>0000-0002-1511-5033 ; 0000-0001-9266-6624 ; 0000-0002-9622-090X ; 0000-0003-1818-0612</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,777,781,27905,27906</link.rule.ids></links><search><creatorcontrib>Zhang, Ben</creatorcontrib><creatorcontrib>Zhou, Yang</creatorcontrib><creatorcontrib>Huang, Hao-Yi</creatorcontrib><creatorcontrib>Zhang, Xiao-Le</creatorcontrib><creatorcontrib>Xiang, Yi</creatorcontrib><creatorcontrib>Shi, Yanbo</creatorcontrib><creatorcontrib>Zhang, Chennan</creatorcontrib><creatorcontrib>Yuan, Aihua</creatorcontrib><creatorcontrib>Cai, Xingwei</creatorcontrib><creatorcontrib>Chen, Lei</creatorcontrib><creatorcontrib>Zhang, Yi-Quan</creatorcontrib><creatorcontrib>Hu, Zhao-Bo</creatorcontrib><title>Effects of weak intramolecular interactions and distortions from trigonal prismatic coordination on the magnetic properties of zero-field Co() single-ion magnets</title><title>Inorganic chemistry frontiers</title><description>The mononuclear cobalt(
ii
) complexes [Co(L
N8
)](BPh
4
)
2
·C
4
H
10
O (
1-BPh
4
) and [Co(L
N8
)](NO
3
)
2
·CH
3
CN (
2-NO
3
) (L
N8
= 1,4,7,10-tetrakis(2-pyridinemethyl)-1,4,7,10-tetraaza-cyclododecane) have been synthesized and fully characterized. They differ well beyond a formal replacement of the counter anions, with their Co(
ii
) centers in significantly different coordination geometries. In
1-BPh
4
, the Co(
ii
) ion is not only coordinated by six N atoms from the L
N8
ligand but also associated with the two remaining N atoms of L
N8
via
weak interactions. In contrast, the Co(
ii
) ion in
2-NO
3
is only six-coordinated in a distorted trigonal prismatic geometry. Magnetic anisotropy and slow magnetic dynamics are drastically affected by these different environments around Co(
ii
). The combination of dc magnetic data, high-frequency and -field electron paramagnetic resonance (HFEPR) and theoretical calculations unambiguously reveals large negative zero-field split (ZFS) parameters
D
for both complexes and a large difference between the
D
values. Both
1-BPh
4
and
2-NO
3
show slow magnetic relaxation at zero field. Magnetic dilution experiments reveal effective energy barriers of 54(4) cm
−1
for
1-BPh
4
@Zn
and 95(5) cm
−1
for
2-NO
3
@Zn
and confirm that the slow magnetic relaxation for both complexes originates from single molecule behaviour.
Ab initio
computational studies explain their electronic structures and the origin of the large negative magnetic anisotropy; they support the corresponding experimental observations. Further magneto-structural analyses reveal that different distortions from the ideal trigonal prismatic geometry exert drastic effects on
D
values and slow relaxation, and that the additional weak intramolecular interactions between Co and N reduce the axial anisotropy.
The change of counter anions significantly affects the environment around Co(
ii
) ions, leading to two zero-field single-ion magnets possessing different uniaxial anisotropies and dynamic magnetic properties.</description><subject>Anisotropy</subject><subject>Cobalt compounds</subject><subject>Coordination</subject><subject>Dilution</subject><subject>Electron paramagnetic resonance</subject><subject>Magnetic anisotropy</subject><subject>Magnetic induction</subject><subject>Magnetic properties</subject><subject>Magnetic relaxation</subject><subject>Magnets</subject><subject>Mathematical analysis</subject><issn>2052-1553</issn><issn>2052-1545</issn><issn>2052-1553</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNpNkd9LwzAQx4MoOOZefBcCvqhQzY82ax_HnDoYiKDPJUsuM7NttiRD9L_xP7VdRYWDu-M-94svQqeUXFPCixvNt5awjIzlARowkrGEZhk__Bcfo1EIa0IIpSmhggzQ18wYUDFgZ_A7yDdsm-hl7SpQu0r6LgUvVbSuCVg2GmsbovN9bryrcfR25RpZ4Y23oZbRKqyc89o2sqNwa_EVcC1XDXTFjXcbaAfAfucneJcYC5XGU3dxiYNtVhUkXWPfEU7QkZFVgNGPH6KXu9nz9CFZPN7Pp5NFolhOYyKMHotC5DBeFhoML1ItcqPyMQGidK6ZSAstcyaXTDPGU6GXWSpAKWmMNIryITrv57YHbncQYrl2O98-FkpO0pyzIkt5S131lPIuBA-mbN-upf8oKSk7Fcpb_jTfqzBp4bMe9kH9cn8q8W918Iim</recordid><startdate>20240430</startdate><enddate>20240430</enddate><creator>Zhang, Ben</creator><creator>Zhou, Yang</creator><creator>Huang, Hao-Yi</creator><creator>Zhang, Xiao-Le</creator><creator>Xiang, Yi</creator><creator>Shi, Yanbo</creator><creator>Zhang, Chennan</creator><creator>Yuan, Aihua</creator><creator>Cai, Xingwei</creator><creator>Chen, Lei</creator><creator>Zhang, Yi-Quan</creator><creator>Hu, Zhao-Bo</creator><general>Royal Society of Chemistry</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><orcidid>https://orcid.org/0000-0002-1511-5033</orcidid><orcidid>https://orcid.org/0000-0001-9266-6624</orcidid><orcidid>https://orcid.org/0000-0002-9622-090X</orcidid><orcidid>https://orcid.org/0000-0003-1818-0612</orcidid></search><sort><creationdate>20240430</creationdate><title>Effects of weak intramolecular interactions and distortions from trigonal prismatic coordination on the magnetic properties of zero-field Co() single-ion magnets</title><author>Zhang, Ben ; Zhou, Yang ; Huang, Hao-Yi ; Zhang, Xiao-Le ; Xiang, Yi ; Shi, Yanbo ; Zhang, Chennan ; Yuan, Aihua ; Cai, Xingwei ; Chen, Lei ; Zhang, Yi-Quan ; Hu, Zhao-Bo</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c281t-6fd76968e7b9def394d68fc870e0cd8d2649da82ab2d22346db546eccaffafc13</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Anisotropy</topic><topic>Cobalt compounds</topic><topic>Coordination</topic><topic>Dilution</topic><topic>Electron paramagnetic resonance</topic><topic>Magnetic anisotropy</topic><topic>Magnetic induction</topic><topic>Magnetic properties</topic><topic>Magnetic relaxation</topic><topic>Magnets</topic><topic>Mathematical analysis</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zhang, Ben</creatorcontrib><creatorcontrib>Zhou, Yang</creatorcontrib><creatorcontrib>Huang, Hao-Yi</creatorcontrib><creatorcontrib>Zhang, Xiao-Le</creatorcontrib><creatorcontrib>Xiang, Yi</creatorcontrib><creatorcontrib>Shi, Yanbo</creatorcontrib><creatorcontrib>Zhang, Chennan</creatorcontrib><creatorcontrib>Yuan, Aihua</creatorcontrib><creatorcontrib>Cai, Xingwei</creatorcontrib><creatorcontrib>Chen, Lei</creatorcontrib><creatorcontrib>Zhang, Yi-Quan</creatorcontrib><creatorcontrib>Hu, Zhao-Bo</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Inorganic chemistry frontiers</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Zhang, Ben</au><au>Zhou, Yang</au><au>Huang, Hao-Yi</au><au>Zhang, Xiao-Le</au><au>Xiang, Yi</au><au>Shi, Yanbo</au><au>Zhang, Chennan</au><au>Yuan, Aihua</au><au>Cai, Xingwei</au><au>Chen, Lei</au><au>Zhang, Yi-Quan</au><au>Hu, Zhao-Bo</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Effects of weak intramolecular interactions and distortions from trigonal prismatic coordination on the magnetic properties of zero-field Co() single-ion magnets</atitle><jtitle>Inorganic chemistry frontiers</jtitle><date>2024-04-30</date><risdate>2024</risdate><volume>11</volume><issue>9</issue><spage>2648</spage><epage>266</epage><pages>2648-266</pages><issn>2052-1553</issn><issn>2052-1545</issn><eissn>2052-1553</eissn><abstract>The mononuclear cobalt(
ii
) complexes [Co(L
N8
)](BPh
4
)
2
·C
4
H
10
O (
1-BPh
4
) and [Co(L
N8
)](NO
3
)
2
·CH
3
CN (
2-NO
3
) (L
N8
= 1,4,7,10-tetrakis(2-pyridinemethyl)-1,4,7,10-tetraaza-cyclododecane) have been synthesized and fully characterized. They differ well beyond a formal replacement of the counter anions, with their Co(
ii
) centers in significantly different coordination geometries. In
1-BPh
4
, the Co(
ii
) ion is not only coordinated by six N atoms from the L
N8
ligand but also associated with the two remaining N atoms of L
N8
via
weak interactions. In contrast, the Co(
ii
) ion in
2-NO
3
is only six-coordinated in a distorted trigonal prismatic geometry. Magnetic anisotropy and slow magnetic dynamics are drastically affected by these different environments around Co(
ii
). The combination of dc magnetic data, high-frequency and -field electron paramagnetic resonance (HFEPR) and theoretical calculations unambiguously reveals large negative zero-field split (ZFS) parameters
D
for both complexes and a large difference between the
D
values. Both
1-BPh
4
and
2-NO
3
show slow magnetic relaxation at zero field. Magnetic dilution experiments reveal effective energy barriers of 54(4) cm
−1
for
1-BPh
4
@Zn
and 95(5) cm
−1
for
2-NO
3
@Zn
and confirm that the slow magnetic relaxation for both complexes originates from single molecule behaviour.
Ab initio
computational studies explain their electronic structures and the origin of the large negative magnetic anisotropy; they support the corresponding experimental observations. Further magneto-structural analyses reveal that different distortions from the ideal trigonal prismatic geometry exert drastic effects on
D
values and slow relaxation, and that the additional weak intramolecular interactions between Co and N reduce the axial anisotropy.
The change of counter anions significantly affects the environment around Co(
ii
) ions, leading to two zero-field single-ion magnets possessing different uniaxial anisotropies and dynamic magnetic properties.</abstract><cop>London</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d3qi02507a</doi><tpages>13</tpages><orcidid>https://orcid.org/0000-0002-1511-5033</orcidid><orcidid>https://orcid.org/0000-0001-9266-6624</orcidid><orcidid>https://orcid.org/0000-0002-9622-090X</orcidid><orcidid>https://orcid.org/0000-0003-1818-0612</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 2052-1553 |
| ispartof | Inorganic chemistry frontiers, 2024-04, Vol.11 (9), p.2648-266 |
| issn | 2052-1553 2052-1545 2052-1553 |
| language | eng |
| recordid | cdi_crossref_primary_10_1039_D3QI02507A |
| source | Royal Society Of Chemistry Journals 2008- |
| subjects | Anisotropy Cobalt compounds Coordination Dilution Electron paramagnetic resonance Magnetic anisotropy Magnetic induction Magnetic properties Magnetic relaxation Magnets Mathematical analysis |
| title | Effects of weak intramolecular interactions and distortions from trigonal prismatic coordination on the magnetic properties of zero-field Co() single-ion magnets |
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