4.5 Article

Investigation on structurally different Cu(II) and Ni(II) complexes constructed from a novel pyridine-terminal salamo-like ligand

Journal

INORGANICA CHIMICA ACTA
Volume 516, Issue -, Pages -

Publisher

ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2020.120095

Keywords

Salamo-like ligand; Complex; TGA analysis; Hirshfeld surface analysis; MOF

Funding

  1. National Natural Science Foundation of China [21968032]
  2. Special Funds for Discipline Construction of Gansu Agricultural University [LXYXK201801]
  3. Program for Excellent Team of Scientific Research in Lanzhou Jiaotong University [201706]

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A novel structurally characterized salamo-like ligand H2L has been designed and synthesized, leading to the formation of Cu(II) and Ni(II) complexes. The Cu(II) complex shows a four-coordinated twisted quadrilateral geometry, while the Ni(II) complex exhibits a slightly distorted octahedral geometry with six-coordination, resulting in the formation of chiral MOFs. Spectroscopic analyses and magnetic analyses were carried out to study the properties of these complexes.
A novel structurally characterized salamo-like ligand H2L contained double terminal pyridine groups was designed and synthesized. The single crystals of the Cu(II) and Ni(II) complexes are grown up through coordination of H2L with Cu(II) and Ni(II) ions, respectively, determined as [Cu(LH)]NO3 center dot CH3CH2OH and [{Ni (L)}(2)](n)center dot n3C(5)H(5) MnCH3COCH3. The Cu(II) atom is located at the N2O2 cavity of the depmtonation ligand (L-2)-moiety, but the N atoms of the terminal pyridine groups of the ligand (L)(2-) moiety is not involved in the coordination, and forms a four-coordinated twisted quadrilateral geometry. While the Ni(II) atom (Ni1 or Ni2) is sited in the N2O2 cavity of the deprotonation ligand (L)(2-) moiety and forms a plane, the terminal pyridine N atoms from the two adjacent [Ni(L)] moieties also coordinated with the Ni(II) atom in the axial positions to form a slightly distorted octahedral geometry with six-coordination. In the formation of MOFs, the benzene and pyridine rings of the ligand (L)(2-)moiety are rotated and create an angle, result to form a chiral MOFs using an achiral ligand (L)(2-) moiety. View of MOFs in the C direction, the Ni(II) complex has four different size of apertures in its structure, and presences a large amount of protonic hydrogen. Spectroscopic analyses of H2L and its Cu(II) and Ni(II) complexes are performed using IR, UV-Vis and fluorescence spectroscopy. Compared with the Cu(II) complex, the Ni(II) complex has better thermal stability. The magnetic analyses were also carried out. Hirshfeld surfaces analyses are carried out to analyze various short-range interactions in H2L and its Cu(II) complex.

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