Crystal design of monometallic single-molecule magnets consisting of cobalt-aminoxyl heterospins

Shinji Kanegawa, Satoru Karasawa, Masataka Maeyama, Motohiro Nakano, Noboru Koga

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Abstract

Five N-aryl-N-pyridylaminoxyls, which have no substituent (PhNOpy), one substituent (MeOPh-NOpy and tert-BuPhNOpy) at the 4-position, and three substituents (TPPNOpy and TBPNOpy) at the 2, 4, and 6-positions of the phenyl ring, were prepared as new ligands for cobalt-aminoxyl heterospin systems. The 1:4 complexes, [Co(NCS)2(PhNOpy)4] (1), [Co(NCS) 2(MeOPhNOpy)4] (2), [Co(NCS)2(tertBuPhNOpy) 4] (3), [Co(NCS)2(TPPNOpy)4] (4), [Co(NCS) 2(TBPNOpy)4] (5a), and [Co(NCO)2(TBPNOpy) 4] (5b), were obtained as single crystals. The molecular geometry revealed by X-ray crystallography for all complexes except 4 is a compressed octahedron. In the crystal structure of 1, 2, and 3, the organic spin centers have various short contacts within 4 Å with the neighboring molecules to form 3D and 2D spin networks. On the other hand, complexes 5a and 5b have no significant short intermolecular contacts, indicating that they are magnetically isolated. 1 and 2 behaved as a 3D antiferromagnet with a Neel temperature, TN, of 22 K and as a weak 3D antiferromagnet with a TN of 2.9 K and a spin-flop field at 1.9 K, Hsp(1.9), of 0.7 kOe, respectively. 3 was a canted 2D antiferromagnet (a weak ferromagnet) with T N = 4.8 K and showed a hysteresis loop with a coercive force, H c, of 1.3 kOe at 1.9 K. On the other hand, the trisubstituted complexes 4, 5a, and 5b functioned as single-molecule magnets (SMMs). 5b had an effective activation barrier, Ueff, value of 28 K in a microcrystalline state and 48 K in a frozen solution.

Original languageEnglish
Pages (from-to)3079-3094
Number of pages16
JournalJournal of the American Chemical Society
Volume130
Issue number10
DOIs
Publication statusPublished - Mar 12 2008

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Magnets
Cobalt
Neel temperature
Crystals
Molecules
X ray crystallography
X Ray Crystallography
Hysteresis loops
Coercive force
Crystal structure
Chemical activation
Ligands
Single crystals
Temperature
Geometry

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Crystal design of monometallic single-molecule magnets consisting of cobalt-aminoxyl heterospins. / Kanegawa, Shinji; Karasawa, Satoru; Maeyama, Masataka; Nakano, Motohiro; Koga, Noboru.

In: Journal of the American Chemical Society, Vol. 130, No. 10, 12.03.2008, p. 3079-3094.

Research output: Contribution to journalArticle

Kanegawa, Shinji ; Karasawa, Satoru ; Maeyama, Masataka ; Nakano, Motohiro ; Koga, Noboru. / Crystal design of monometallic single-molecule magnets consisting of cobalt-aminoxyl heterospins. In: Journal of the American Chemical Society. 2008 ; Vol. 130, No. 10. pp. 3079-3094.
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title = "Crystal design of monometallic single-molecule magnets consisting of cobalt-aminoxyl heterospins",
abstract = "Five N-aryl-N-pyridylaminoxyls, which have no substituent (PhNOpy), one substituent (MeOPh-NOpy and tert-BuPhNOpy) at the 4-position, and three substituents (TPPNOpy and TBPNOpy) at the 2, 4, and 6-positions of the phenyl ring, were prepared as new ligands for cobalt-aminoxyl heterospin systems. The 1:4 complexes, [Co(NCS)2(PhNOpy)4] (1), [Co(NCS) 2(MeOPhNOpy)4] (2), [Co(NCS)2(tertBuPhNOpy) 4] (3), [Co(NCS)2(TPPNOpy)4] (4), [Co(NCS) 2(TBPNOpy)4] (5a), and [Co(NCO)2(TBPNOpy) 4] (5b), were obtained as single crystals. The molecular geometry revealed by X-ray crystallography for all complexes except 4 is a compressed octahedron. In the crystal structure of 1, 2, and 3, the organic spin centers have various short contacts within 4 {\AA} with the neighboring molecules to form 3D and 2D spin networks. On the other hand, complexes 5a and 5b have no significant short intermolecular contacts, indicating that they are magnetically isolated. 1 and 2 behaved as a 3D antiferromagnet with a Neel temperature, TN, of 22 K and as a weak 3D antiferromagnet with a TN of 2.9 K and a spin-flop field at 1.9 K, Hsp(1.9), of 0.7 kOe, respectively. 3 was a canted 2D antiferromagnet (a weak ferromagnet) with T N = 4.8 K and showed a hysteresis loop with a coercive force, H c, of 1.3 kOe at 1.9 K. On the other hand, the trisubstituted complexes 4, 5a, and 5b functioned as single-molecule magnets (SMMs). 5b had an effective activation barrier, Ueff, value of 28 K in a microcrystalline state and 48 K in a frozen solution.",
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T1 - Crystal design of monometallic single-molecule magnets consisting of cobalt-aminoxyl heterospins

AU - Kanegawa, Shinji

AU - Karasawa, Satoru

AU - Maeyama, Masataka

AU - Nakano, Motohiro

AU - Koga, Noboru

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Y1 - 2008/3/12

N2 - Five N-aryl-N-pyridylaminoxyls, which have no substituent (PhNOpy), one substituent (MeOPh-NOpy and tert-BuPhNOpy) at the 4-position, and three substituents (TPPNOpy and TBPNOpy) at the 2, 4, and 6-positions of the phenyl ring, were prepared as new ligands for cobalt-aminoxyl heterospin systems. The 1:4 complexes, [Co(NCS)2(PhNOpy)4] (1), [Co(NCS) 2(MeOPhNOpy)4] (2), [Co(NCS)2(tertBuPhNOpy) 4] (3), [Co(NCS)2(TPPNOpy)4] (4), [Co(NCS) 2(TBPNOpy)4] (5a), and [Co(NCO)2(TBPNOpy) 4] (5b), were obtained as single crystals. The molecular geometry revealed by X-ray crystallography for all complexes except 4 is a compressed octahedron. In the crystal structure of 1, 2, and 3, the organic spin centers have various short contacts within 4 Å with the neighboring molecules to form 3D and 2D spin networks. On the other hand, complexes 5a and 5b have no significant short intermolecular contacts, indicating that they are magnetically isolated. 1 and 2 behaved as a 3D antiferromagnet with a Neel temperature, TN, of 22 K and as a weak 3D antiferromagnet with a TN of 2.9 K and a spin-flop field at 1.9 K, Hsp(1.9), of 0.7 kOe, respectively. 3 was a canted 2D antiferromagnet (a weak ferromagnet) with T N = 4.8 K and showed a hysteresis loop with a coercive force, H c, of 1.3 kOe at 1.9 K. On the other hand, the trisubstituted complexes 4, 5a, and 5b functioned as single-molecule magnets (SMMs). 5b had an effective activation barrier, Ueff, value of 28 K in a microcrystalline state and 48 K in a frozen solution.

AB - Five N-aryl-N-pyridylaminoxyls, which have no substituent (PhNOpy), one substituent (MeOPh-NOpy and tert-BuPhNOpy) at the 4-position, and three substituents (TPPNOpy and TBPNOpy) at the 2, 4, and 6-positions of the phenyl ring, were prepared as new ligands for cobalt-aminoxyl heterospin systems. The 1:4 complexes, [Co(NCS)2(PhNOpy)4] (1), [Co(NCS) 2(MeOPhNOpy)4] (2), [Co(NCS)2(tertBuPhNOpy) 4] (3), [Co(NCS)2(TPPNOpy)4] (4), [Co(NCS) 2(TBPNOpy)4] (5a), and [Co(NCO)2(TBPNOpy) 4] (5b), were obtained as single crystals. The molecular geometry revealed by X-ray crystallography for all complexes except 4 is a compressed octahedron. In the crystal structure of 1, 2, and 3, the organic spin centers have various short contacts within 4 Å with the neighboring molecules to form 3D and 2D spin networks. On the other hand, complexes 5a and 5b have no significant short intermolecular contacts, indicating that they are magnetically isolated. 1 and 2 behaved as a 3D antiferromagnet with a Neel temperature, TN, of 22 K and as a weak 3D antiferromagnet with a TN of 2.9 K and a spin-flop field at 1.9 K, Hsp(1.9), of 0.7 kOe, respectively. 3 was a canted 2D antiferromagnet (a weak ferromagnet) with T N = 4.8 K and showed a hysteresis loop with a coercive force, H c, of 1.3 kOe at 1.9 K. On the other hand, the trisubstituted complexes 4, 5a, and 5b functioned as single-molecule magnets (SMMs). 5b had an effective activation barrier, Ueff, value of 28 K in a microcrystalline state and 48 K in a frozen solution.

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