Structural variability in manganese(II) complexes of N,N′-bis(2-pyridinylmethylene) ethane (and propane) diamine ligands

Iraklii I. Ebralidze, Gregory Leitus, Linda J W Shimon, Yong Wang, Sason Shaik, Ronny Neumann

Research output: Contribution to journalArticle

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Abstract

Manganese(II) complexes, Mn2L1 3(ClO4)4, MnL1(H2O)2(ClO4)2, MnL2(H2O)2(ClO4)2, and {(μ-Cl)MnL2(PF6)}2 based on N,N′-bis(2-pyridinylmethylene) ethanediamine (L1) and N,N′-bis(2-pyridinylmethylene) propanediamine (L2) ligands have been prepared and characterized. The single crystal X-ray diffraction analysis of Mn2L2 3(ClO4)4 shows that each of the two Mn(II) ion centers with a Mn-Mn distance of 7.15 Å are coordinated by one ligand while a common third ligand bridges the metal centers. Solid-state magnetic susceptibility measurements as well as DFT calculations confirm that each of the manganese centers is high-spin S = 5/2. The electronic structure obtained shows no orbital overlap between the Mn(II) centers indicating that the observed weak antiferromagentism is a result of through space interactions between the two Mn(II) centers. Under different reaction conditions, L1 and Mn(II) yielded a one-dimensional polymer, MnL1(H2O)2(ClO4)2. Ligand L2 when reacted with manganese(II) perchlorate gives contrarily to L1 mononuclear MnL2(H2O)2(ClO4)2 complex. The analysis of the structural properties of the MnL2(H2O)2(ClO4)2 lead to the design of dinuclear complex {(μ-Cl)MnL2(PF6)} where two chlorine atoms were utilized as bridging moieties. This complex has a rhomboidal Mn2Cl2 core with a Mn-Mn distance of 3.726 Å. At room temperature {(μ-Cl)MnL2(PF6)} is ferromagnetic with observed μeff = 4.04 μB per Mn(II) ion. With cooling, μeff grows reaching 4.81 μB per Mn(II) ion at 8 K, and then undergoes ferromagnetic-to-antiferromagnetic phase transition.

Original languageEnglish
Pages (from-to)4713-4720
Number of pages8
JournalInorganica Chimica Acta
Volume362
Issue number13
DOIs
Publication statusPublished - Oct 15 2009

Fingerprint

Propane
Ethane
Diamines
diamines
Manganese
propane
ethane
manganese
Ligands
ligands
Ions
Magnetic susceptibility
ions
Discrete Fourier transforms
X ray diffraction analysis
Chlorine
Electronic structure
Structural properties
perchlorates
Phase transitions

Keywords

  • Amine ligands
  • Manganese(II) complex
  • Schiff base
  • Structure

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Structural variability in manganese(II) complexes of N,N′-bis(2-pyridinylmethylene) ethane (and propane) diamine ligands. / Ebralidze, Iraklii I.; Leitus, Gregory; Shimon, Linda J W; Wang, Yong; Shaik, Sason; Neumann, Ronny.

In: Inorganica Chimica Acta, Vol. 362, No. 13, 15.10.2009, p. 4713-4720.

Research output: Contribution to journalArticle

Ebralidze, Iraklii I. ; Leitus, Gregory ; Shimon, Linda J W ; Wang, Yong ; Shaik, Sason ; Neumann, Ronny. / Structural variability in manganese(II) complexes of N,N′-bis(2-pyridinylmethylene) ethane (and propane) diamine ligands. In: Inorganica Chimica Acta. 2009 ; Vol. 362, No. 13. pp. 4713-4720.
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title = "Structural variability in manganese(II) complexes of N,N′-bis(2-pyridinylmethylene) ethane (and propane) diamine ligands",
abstract = "Manganese(II) complexes, Mn2L1 3(ClO4)4, MnL1(H2O)2(ClO4)2, MnL2(H2O)2(ClO4)2, and {(μ-Cl)MnL2(PF6)}2 based on N,N′-bis(2-pyridinylmethylene) ethanediamine (L1) and N,N′-bis(2-pyridinylmethylene) propanediamine (L2) ligands have been prepared and characterized. The single crystal X-ray diffraction analysis of Mn2L2 3(ClO4)4 shows that each of the two Mn(II) ion centers with a Mn-Mn distance of 7.15 {\AA} are coordinated by one ligand while a common third ligand bridges the metal centers. Solid-state magnetic susceptibility measurements as well as DFT calculations confirm that each of the manganese centers is high-spin S = 5/2. The electronic structure obtained shows no orbital overlap between the Mn(II) centers indicating that the observed weak antiferromagentism is a result of through space interactions between the two Mn(II) centers. Under different reaction conditions, L1 and Mn(II) yielded a one-dimensional polymer, MnL1(H2O)2(ClO4)2. Ligand L2 when reacted with manganese(II) perchlorate gives contrarily to L1 mononuclear MnL2(H2O)2(ClO4)2 complex. The analysis of the structural properties of the MnL2(H2O)2(ClO4)2 lead to the design of dinuclear complex {(μ-Cl)MnL2(PF6)} where two chlorine atoms were utilized as bridging moieties. This complex has a rhomboidal Mn2Cl2 core with a Mn-Mn distance of 3.726 {\AA}. At room temperature {(μ-Cl)MnL2(PF6)} is ferromagnetic with observed μeff = 4.04 μB per Mn(II) ion. With cooling, μeff grows reaching 4.81 μB per Mn(II) ion at 8 K, and then undergoes ferromagnetic-to-antiferromagnetic phase transition.",
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T1 - Structural variability in manganese(II) complexes of N,N′-bis(2-pyridinylmethylene) ethane (and propane) diamine ligands

AU - Ebralidze, Iraklii I.

AU - Leitus, Gregory

AU - Shimon, Linda J W

AU - Wang, Yong

AU - Shaik, Sason

AU - Neumann, Ronny

PY - 2009/10/15

Y1 - 2009/10/15

N2 - Manganese(II) complexes, Mn2L1 3(ClO4)4, MnL1(H2O)2(ClO4)2, MnL2(H2O)2(ClO4)2, and {(μ-Cl)MnL2(PF6)}2 based on N,N′-bis(2-pyridinylmethylene) ethanediamine (L1) and N,N′-bis(2-pyridinylmethylene) propanediamine (L2) ligands have been prepared and characterized. The single crystal X-ray diffraction analysis of Mn2L2 3(ClO4)4 shows that each of the two Mn(II) ion centers with a Mn-Mn distance of 7.15 Å are coordinated by one ligand while a common third ligand bridges the metal centers. Solid-state magnetic susceptibility measurements as well as DFT calculations confirm that each of the manganese centers is high-spin S = 5/2. The electronic structure obtained shows no orbital overlap between the Mn(II) centers indicating that the observed weak antiferromagentism is a result of through space interactions between the two Mn(II) centers. Under different reaction conditions, L1 and Mn(II) yielded a one-dimensional polymer, MnL1(H2O)2(ClO4)2. Ligand L2 when reacted with manganese(II) perchlorate gives contrarily to L1 mononuclear MnL2(H2O)2(ClO4)2 complex. The analysis of the structural properties of the MnL2(H2O)2(ClO4)2 lead to the design of dinuclear complex {(μ-Cl)MnL2(PF6)} where two chlorine atoms were utilized as bridging moieties. This complex has a rhomboidal Mn2Cl2 core with a Mn-Mn distance of 3.726 Å. At room temperature {(μ-Cl)MnL2(PF6)} is ferromagnetic with observed μeff = 4.04 μB per Mn(II) ion. With cooling, μeff grows reaching 4.81 μB per Mn(II) ion at 8 K, and then undergoes ferromagnetic-to-antiferromagnetic phase transition.

AB - Manganese(II) complexes, Mn2L1 3(ClO4)4, MnL1(H2O)2(ClO4)2, MnL2(H2O)2(ClO4)2, and {(μ-Cl)MnL2(PF6)}2 based on N,N′-bis(2-pyridinylmethylene) ethanediamine (L1) and N,N′-bis(2-pyridinylmethylene) propanediamine (L2) ligands have been prepared and characterized. The single crystal X-ray diffraction analysis of Mn2L2 3(ClO4)4 shows that each of the two Mn(II) ion centers with a Mn-Mn distance of 7.15 Å are coordinated by one ligand while a common third ligand bridges the metal centers. Solid-state magnetic susceptibility measurements as well as DFT calculations confirm that each of the manganese centers is high-spin S = 5/2. The electronic structure obtained shows no orbital overlap between the Mn(II) centers indicating that the observed weak antiferromagentism is a result of through space interactions between the two Mn(II) centers. Under different reaction conditions, L1 and Mn(II) yielded a one-dimensional polymer, MnL1(H2O)2(ClO4)2. Ligand L2 when reacted with manganese(II) perchlorate gives contrarily to L1 mononuclear MnL2(H2O)2(ClO4)2 complex. The analysis of the structural properties of the MnL2(H2O)2(ClO4)2 lead to the design of dinuclear complex {(μ-Cl)MnL2(PF6)} where two chlorine atoms were utilized as bridging moieties. This complex has a rhomboidal Mn2Cl2 core with a Mn-Mn distance of 3.726 Å. At room temperature {(μ-Cl)MnL2(PF6)} is ferromagnetic with observed μeff = 4.04 μB per Mn(II) ion. With cooling, μeff grows reaching 4.81 μB per Mn(II) ion at 8 K, and then undergoes ferromagnetic-to-antiferromagnetic phase transition.

KW - Amine ligands

KW - Manganese(II) complex

KW - Schiff base

KW - Structure

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EP - 4720

JO - Inorganica Chimica Acta

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