Synthesis, crystal structures and electronic properties of Schiff base nickel (II) complexes: Towards solvatochromism induced by a photochromic solute

Takashiro Akitsu, Yasuaki Einaga

Research output: Contribution to journalArticle

85 Citations (Scopus)

Abstract

Two new mononuclear nickel (II) complexes incorporating Schiff base ligands, bis(N-R-1-phenylethyl- or N-2-propyl-3,5-dichlorosalicydenaminato) nickel (II), have been synthesized and characterized. The former chiral brown paramagnetic complex adopts a compressed tetrahedral [NiN2O 2] coordination geometry of Λ(R,R) absolute configuration with the coordination bond angles of N-Ni-N = 116.3(2)°and O-Ni-O = 141.4(2)°. On the other hand, the latter green diamagnetic complex adopts a square planar trans-[NiN2O2] coordination geometry. It is revealed that flexible distortion of the [NiN2O2] coordination environment and the overall dipole moment of the complexes are affected by both electronic withdrawing Cl-substituents and steric factors of the ligands. A structural phase transition occurs by heating in the solid state for both complexes. Negative solvatochromism relating to d-d and π-π* transitions can be observed, depending on the polarity of the solvents in which these complexes are dissolved. Furthermore, we have attempted to design a supramolecular solvatochromism system induced by a photochromic solute, that is a CHCl3 solution of the chiral Ni(II) complex and polar 4-hydroxyazobenzene solute. After UV light irradiation, we have successfully observed slight spectral changes of the π-π* bands in absorption and CD spectra due to conformational change of the R-1-phenylethylamine moieties of the chiral ligands.

Original languageEnglish
Pages (from-to)1869-1877
Number of pages9
JournalPolyhedron
Volume24
Issue number14
DOIs
Publication statusPublished - 2005 Oct 3

Fingerprint

Schiff Bases
Nickel
Electronic properties
imines
solutes
Crystal structure
Ligands
nickel
crystal structure
synthesis
electronics
ligands
Phenethylamines
Geometry
Phase Transition
Dipole moment
Ultraviolet Rays
Ultraviolet radiation
Heating
geometry

Keywords

  • Chirality
  • Crystal structures
  • Nickel (II) complexes
  • Schiff base
  • Solvatochromism

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Synthesis, crystal structures and electronic properties of Schiff base nickel (II) complexes : Towards solvatochromism induced by a photochromic solute. / Akitsu, Takashiro; Einaga, Yasuaki.

In: Polyhedron, Vol. 24, No. 14, 03.10.2005, p. 1869-1877.

Research output: Contribution to journalArticle

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N2 - Two new mononuclear nickel (II) complexes incorporating Schiff base ligands, bis(N-R-1-phenylethyl- or N-2-propyl-3,5-dichlorosalicydenaminato) nickel (II), have been synthesized and characterized. The former chiral brown paramagnetic complex adopts a compressed tetrahedral [NiN2O 2] coordination geometry of Λ(R,R) absolute configuration with the coordination bond angles of N-Ni-N = 116.3(2)°and O-Ni-O = 141.4(2)°. On the other hand, the latter green diamagnetic complex adopts a square planar trans-[NiN2O2] coordination geometry. It is revealed that flexible distortion of the [NiN2O2] coordination environment and the overall dipole moment of the complexes are affected by both electronic withdrawing Cl-substituents and steric factors of the ligands. A structural phase transition occurs by heating in the solid state for both complexes. Negative solvatochromism relating to d-d and π-π* transitions can be observed, depending on the polarity of the solvents in which these complexes are dissolved. Furthermore, we have attempted to design a supramolecular solvatochromism system induced by a photochromic solute, that is a CHCl3 solution of the chiral Ni(II) complex and polar 4-hydroxyazobenzene solute. After UV light irradiation, we have successfully observed slight spectral changes of the π-π* bands in absorption and CD spectra due to conformational change of the R-1-phenylethylamine moieties of the chiral ligands.

AB - Two new mononuclear nickel (II) complexes incorporating Schiff base ligands, bis(N-R-1-phenylethyl- or N-2-propyl-3,5-dichlorosalicydenaminato) nickel (II), have been synthesized and characterized. The former chiral brown paramagnetic complex adopts a compressed tetrahedral [NiN2O 2] coordination geometry of Λ(R,R) absolute configuration with the coordination bond angles of N-Ni-N = 116.3(2)°and O-Ni-O = 141.4(2)°. On the other hand, the latter green diamagnetic complex adopts a square planar trans-[NiN2O2] coordination geometry. It is revealed that flexible distortion of the [NiN2O2] coordination environment and the overall dipole moment of the complexes are affected by both electronic withdrawing Cl-substituents and steric factors of the ligands. A structural phase transition occurs by heating in the solid state for both complexes. Negative solvatochromism relating to d-d and π-π* transitions can be observed, depending on the polarity of the solvents in which these complexes are dissolved. Furthermore, we have attempted to design a supramolecular solvatochromism system induced by a photochromic solute, that is a CHCl3 solution of the chiral Ni(II) complex and polar 4-hydroxyazobenzene solute. After UV light irradiation, we have successfully observed slight spectral changes of the π-π* bands in absorption and CD spectra due to conformational change of the R-1-phenylethylamine moieties of the chiral ligands.

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