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Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
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High-spin Ni(II) clusters: triangles and planar tetranuclear complexes.

Athanassios D Katsenis1, Vadim G Kessler, Giannis S Papaefstathiou

  • 1Laboratory of Inorganic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis, 157 71, Zografou, Greece.

Dalton Transactions (Cambridge, England : 2003)
|March 25, 2011
PubMed
Summary
This summary is machine-generated.

This study synthesized novel nickel complexes, revealing that halide anion size dictates whether tetranuclear or trinuclear structures form, influencing their magnetic properties.

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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
10:51

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Published on: April 10, 2015

Area of Science:

  • Coordination Chemistry
  • Inorganic Chemistry
  • Materials Science

Background:

  • The NiX(2)/di-2-pyridyl ketone/triethylamine reaction system is explored.
  • Previous studies have not fully elucidated the structural diversity and magnetic behavior of nickel complexes derived from this system.

Purpose of the Study:

  • To synthesize and characterize novel nickel aggregates using the NiX(2)/py(2)CO/Et(3)N system.
  • To investigate the influence of halide anions (X = F, Cl, Br, I) on the nuclearity and topology of the resulting nickel complexes.
  • To study the magnetic properties of the synthesized complexes.

Main Methods:

  • Synthesis of nickel complexes via the NiX(2)/py(2)CO/Et(3)N reaction.
  • Single-crystal X-ray diffraction for structural determination.
  • Variable-temperature direct current (dc) and alternating current (ac) magnetic susceptibility measurements.
  • Magnetization measurements.

Main Results:

  • Tetranuclear complexes ([Ni(4)Cl(2){py(2)C(OH)O}(2){py(2)C(OMe)O}(2)(MeOH)(2)]Cl(2) and [Ni(4)Br(2){py(2)C(OH)O}(2){py(2)C(OMe)O}(2)(MeOH)(2)]Br(2)) were formed with intermediate-sized Cl(-) and Br(-) anions, exhibiting planar structures with tetramolybdate topology.
  • Trinuclear complexes ([Ni(3){py(2)C(OMe)O}(4)]I(2), [Ni(3){py(2)C(OMe)O}(4)](NO(3))(0.65)I(1.35), and [Ni(3){py(2)C(OMe)O}(4)](SiF(6))(0.8)F(0.4)) were obtained with smaller F(-) and larger I(-) anions, adopting triangular structures with isosceles topology.
  • Complexes 1-3 were found to be high-spin, with ground states S = 4 for the tetranuclear complexes and S = 3 for the trinuclear complex.

Conclusions:

  • The size of the halide anion is a critical factor in directing the self-assembly of nickel complexes, leading to distinct tetranuclear or trinuclear structures.
  • The observed structural motifs (planar tetranuclear vs. triangular trinuclear) are correlated with the nature of the halide counterions.
  • The synthesized nickel complexes display interesting magnetic properties, with high-spin ground states dependent on their nuclearity.