Wheel-Shaped Icosanuclear Homo- and Heterometallic Complexes of Ni II, Co II, and Cu II ions supported by unsymmetrical aminoalcohol ligands

Takayuki Nakajima, Keiko Seto, Fumihiro Horikawa, Isao Shimizu, Andreas Scheurer, Bunsho Kure, Takashi Kajiwara, Tomoaki Tanase, Masahiro Mikuriya

Research output: Contribution to journalArticle

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Abstract

Reactions of M(OAc) 2·4H 2O (M = Ni, Co) with 3-[benzyl(2-hydroxyethyl)amino]-1-propanol (H 2L) in the presence of pyridine or triethylamine afforded novel homometallic icosanuclear wheel-shaped complexes [M 20L 4(HL) 4(OAc) 28] (M = Ni (1), Co (2)), which consist of a central M II 12 single-stranded, nearly planar loop with four peripheral [M 2(HL)(OAc) 2] fragments attached in an S 4 symmetrical fashion. The complexes can alternatively be recognized as saddle-shaped wheel structures, in which four tetranuclear units of [M 4L(HL)(OAc) 7] 2- are connected by four M 2+ ions (M5). The tetranuclear unit itself can be derived from an ideal C 2 symmetrical [M 4(HL) 2(μ-η 2-OAc) 4(μ- η 11-OAc) 21, η 1-OAc)] - structure through deprotonation of the HL - ligand, and is composed of two plane-shared M 3O 4 incomplete cubanes in which the M2 and M3 atoms are involved in the central fused plane and the M1 and M4 atoms are disposed at the apex sites. Mixed-metal icosanuclear complexes [Ni xM 20-xL 4(HL) 4(OAc) 28] (3, M = Co, x = 9.5) and [Ni 12M 8L 4(HL) 4(OAc) 28] (4, M = Cu) were also synthesized by using equimolar amounts of Ni II and M II ions, and were shown to have similar structures to 1 and 2. X-ray crystallographic and fluorescent analyses revealed that complex 3 contains nonstoichiometric amounts of Ni 2+ and Co 2+ ions in the ratio of 9.5:10.5 and that these are disordered at every metal site. In striking contrast, complex 4 has a stoichiometric formula of Ni 12Cu 8, which was confirmed by the Jahn-Teller elongation of Cu 2+ ions, and consequently, the M2 and M5 positions are occupied exclusively by the Cu 2+ ions. The temperature-dependent direct current (dc) magnetic susceptibility data showed the presence of ferromagnetic exchange interactions in the Ni homometallic (1) and NiCu bimetallic (4) complexes, while the Co homometallic (2) and NiCo bimetallic (3) complexes exhibited antiferromagnetic interactions due to spin-orbit coupling effects of the octahedral Co II ions. The present results demonstrate that the unsymmetrical aminoalcohol ligand H 2L is quite effective in organizing the homo- and heterometallic icosanuclear wheel-shaped metal arrangements.

Original languageEnglish
Pages (from-to)12503-12510
Number of pages8
JournalInorganic Chemistry
Volume51
Issue number22
DOIs
Publication statusPublished - 2012 Nov 19

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wheels
Wheels
Ions
Ligands
ligands
ions
Metals
metals
cubane
1-Propanol
Atoms
Deprotonation
Coordination Complexes
Exchange interactions
saddles
organizing
Magnetic susceptibility
elongation
atoms
Elongation

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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Wheel-Shaped Icosanuclear Homo- and Heterometallic Complexes of Ni II, Co II, and Cu II ions supported by unsymmetrical aminoalcohol ligands. / Nakajima, Takayuki; Seto, Keiko; Horikawa, Fumihiro; Shimizu, Isao; Scheurer, Andreas; Kure, Bunsho; Kajiwara, Takashi; Tanase, Tomoaki; Mikuriya, Masahiro.

In: Inorganic Chemistry, Vol. 51, No. 22, 19.11.2012, p. 12503-12510.

Research output: Contribution to journalArticle

Nakajima, T, Seto, K, Horikawa, F, Shimizu, I, Scheurer, A, Kure, B, Kajiwara, T, Tanase, T & Mikuriya, M 2012, 'Wheel-Shaped Icosanuclear Homo- and Heterometallic Complexes of Ni II, Co II, and Cu II ions supported by unsymmetrical aminoalcohol ligands', Inorganic Chemistry, vol. 51, no. 22, pp. 12503-12510. https://doi.org/10.1021/ic3019106
Nakajima, Takayuki ; Seto, Keiko ; Horikawa, Fumihiro ; Shimizu, Isao ; Scheurer, Andreas ; Kure, Bunsho ; Kajiwara, Takashi ; Tanase, Tomoaki ; Mikuriya, Masahiro. / Wheel-Shaped Icosanuclear Homo- and Heterometallic Complexes of Ni II, Co II, and Cu II ions supported by unsymmetrical aminoalcohol ligands. In: Inorganic Chemistry. 2012 ; Vol. 51, No. 22. pp. 12503-12510.
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title = "Wheel-Shaped Icosanuclear Homo- and Heterometallic Complexes of Ni II, Co II, and Cu II ions supported by unsymmetrical aminoalcohol ligands",
abstract = "Reactions of M(OAc) 2·4H 2O (M = Ni, Co) with 3-[benzyl(2-hydroxyethyl)amino]-1-propanol (H 2L) in the presence of pyridine or triethylamine afforded novel homometallic icosanuclear wheel-shaped complexes [M 20L 4(HL) 4(OAc) 28] (M = Ni (1), Co (2)), which consist of a central M II 12 single-stranded, nearly planar loop with four peripheral [M 2(HL)(OAc) 2] fragments attached in an S 4 symmetrical fashion. The complexes can alternatively be recognized as saddle-shaped wheel structures, in which four tetranuclear units of [M 4L(HL)(OAc) 7] 2- are connected by four M 2+ ions (M5). The tetranuclear unit itself can be derived from an ideal C 2 symmetrical [M 4(HL) 2(μ-η 2-OAc) 4(μ- η 1,η 1-OAc) 2(η 1, η 1-OAc)] - structure through deprotonation of the HL - ligand, and is composed of two plane-shared M 3O 4 incomplete cubanes in which the M2 and M3 atoms are involved in the central fused plane and the M1 and M4 atoms are disposed at the apex sites. Mixed-metal icosanuclear complexes [Ni xM 20-xL 4(HL) 4(OAc) 28] (3, M = Co, x = 9.5) and [Ni 12M 8L 4(HL) 4(OAc) 28] (4, M = Cu) were also synthesized by using equimolar amounts of Ni II and M II ions, and were shown to have similar structures to 1 and 2. X-ray crystallographic and fluorescent analyses revealed that complex 3 contains nonstoichiometric amounts of Ni 2+ and Co 2+ ions in the ratio of 9.5:10.5 and that these are disordered at every metal site. In striking contrast, complex 4 has a stoichiometric formula of Ni 12Cu 8, which was confirmed by the Jahn-Teller elongation of Cu 2+ ions, and consequently, the M2 and M5 positions are occupied exclusively by the Cu 2+ ions. The temperature-dependent direct current (dc) magnetic susceptibility data showed the presence of ferromagnetic exchange interactions in the Ni homometallic (1) and NiCu bimetallic (4) complexes, while the Co homometallic (2) and NiCo bimetallic (3) complexes exhibited antiferromagnetic interactions due to spin-orbit coupling effects of the octahedral Co II ions. The present results demonstrate that the unsymmetrical aminoalcohol ligand H 2L is quite effective in organizing the homo- and heterometallic icosanuclear wheel-shaped metal arrangements.",
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T1 - Wheel-Shaped Icosanuclear Homo- and Heterometallic Complexes of Ni II, Co II, and Cu II ions supported by unsymmetrical aminoalcohol ligands

AU - Nakajima, Takayuki

AU - Seto, Keiko

AU - Horikawa, Fumihiro

AU - Shimizu, Isao

AU - Scheurer, Andreas

AU - Kure, Bunsho

AU - Kajiwara, Takashi

AU - Tanase, Tomoaki

AU - Mikuriya, Masahiro

PY - 2012/11/19

Y1 - 2012/11/19

N2 - Reactions of M(OAc) 2·4H 2O (M = Ni, Co) with 3-[benzyl(2-hydroxyethyl)amino]-1-propanol (H 2L) in the presence of pyridine or triethylamine afforded novel homometallic icosanuclear wheel-shaped complexes [M 20L 4(HL) 4(OAc) 28] (M = Ni (1), Co (2)), which consist of a central M II 12 single-stranded, nearly planar loop with four peripheral [M 2(HL)(OAc) 2] fragments attached in an S 4 symmetrical fashion. The complexes can alternatively be recognized as saddle-shaped wheel structures, in which four tetranuclear units of [M 4L(HL)(OAc) 7] 2- are connected by four M 2+ ions (M5). The tetranuclear unit itself can be derived from an ideal C 2 symmetrical [M 4(HL) 2(μ-η 2-OAc) 4(μ- η 1,η 1-OAc) 2(η 1, η 1-OAc)] - structure through deprotonation of the HL - ligand, and is composed of two plane-shared M 3O 4 incomplete cubanes in which the M2 and M3 atoms are involved in the central fused plane and the M1 and M4 atoms are disposed at the apex sites. Mixed-metal icosanuclear complexes [Ni xM 20-xL 4(HL) 4(OAc) 28] (3, M = Co, x = 9.5) and [Ni 12M 8L 4(HL) 4(OAc) 28] (4, M = Cu) were also synthesized by using equimolar amounts of Ni II and M II ions, and were shown to have similar structures to 1 and 2. X-ray crystallographic and fluorescent analyses revealed that complex 3 contains nonstoichiometric amounts of Ni 2+ and Co 2+ ions in the ratio of 9.5:10.5 and that these are disordered at every metal site. In striking contrast, complex 4 has a stoichiometric formula of Ni 12Cu 8, which was confirmed by the Jahn-Teller elongation of Cu 2+ ions, and consequently, the M2 and M5 positions are occupied exclusively by the Cu 2+ ions. The temperature-dependent direct current (dc) magnetic susceptibility data showed the presence of ferromagnetic exchange interactions in the Ni homometallic (1) and NiCu bimetallic (4) complexes, while the Co homometallic (2) and NiCo bimetallic (3) complexes exhibited antiferromagnetic interactions due to spin-orbit coupling effects of the octahedral Co II ions. The present results demonstrate that the unsymmetrical aminoalcohol ligand H 2L is quite effective in organizing the homo- and heterometallic icosanuclear wheel-shaped metal arrangements.

AB - Reactions of M(OAc) 2·4H 2O (M = Ni, Co) with 3-[benzyl(2-hydroxyethyl)amino]-1-propanol (H 2L) in the presence of pyridine or triethylamine afforded novel homometallic icosanuclear wheel-shaped complexes [M 20L 4(HL) 4(OAc) 28] (M = Ni (1), Co (2)), which consist of a central M II 12 single-stranded, nearly planar loop with four peripheral [M 2(HL)(OAc) 2] fragments attached in an S 4 symmetrical fashion. The complexes can alternatively be recognized as saddle-shaped wheel structures, in which four tetranuclear units of [M 4L(HL)(OAc) 7] 2- are connected by four M 2+ ions (M5). The tetranuclear unit itself can be derived from an ideal C 2 symmetrical [M 4(HL) 2(μ-η 2-OAc) 4(μ- η 1,η 1-OAc) 2(η 1, η 1-OAc)] - structure through deprotonation of the HL - ligand, and is composed of two plane-shared M 3O 4 incomplete cubanes in which the M2 and M3 atoms are involved in the central fused plane and the M1 and M4 atoms are disposed at the apex sites. Mixed-metal icosanuclear complexes [Ni xM 20-xL 4(HL) 4(OAc) 28] (3, M = Co, x = 9.5) and [Ni 12M 8L 4(HL) 4(OAc) 28] (4, M = Cu) were also synthesized by using equimolar amounts of Ni II and M II ions, and were shown to have similar structures to 1 and 2. X-ray crystallographic and fluorescent analyses revealed that complex 3 contains nonstoichiometric amounts of Ni 2+ and Co 2+ ions in the ratio of 9.5:10.5 and that these are disordered at every metal site. In striking contrast, complex 4 has a stoichiometric formula of Ni 12Cu 8, which was confirmed by the Jahn-Teller elongation of Cu 2+ ions, and consequently, the M2 and M5 positions are occupied exclusively by the Cu 2+ ions. The temperature-dependent direct current (dc) magnetic susceptibility data showed the presence of ferromagnetic exchange interactions in the Ni homometallic (1) and NiCu bimetallic (4) complexes, while the Co homometallic (2) and NiCo bimetallic (3) complexes exhibited antiferromagnetic interactions due to spin-orbit coupling effects of the octahedral Co II ions. The present results demonstrate that the unsymmetrical aminoalcohol ligand H 2L is quite effective in organizing the homo- and heterometallic icosanuclear wheel-shaped metal arrangements.

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