Cu(II) complexes with square pyramidal (N2S)CuCl2 chromophore: Jahn-Teller distortion and subsequent effect on spectral and structural properties |
| |
| Authors: | Suprakash Roy Apurba K Patra |
| |
| Institution: | a Department of Chemistry, National Institute of Technology Durgapur, Mahatma Gandhi Avenue, Durgapur 713209, India
b Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, 2A and 2B Raja S.C. Mullick Road, Jadavpur, Kolkata 700032, India |
| |
| Abstract: | One monomeric neutral Cu(II) complex (pmtpm)CuCl2] (1) is reported by Lindoy and Livingstone 8]. Two new complexes namely, μ-Cl bridged binuclear Cu(II) complex {(pmtpm)Cu(Cl)}2 μ-Cl](ClO4) (2) and a bis μ-Cl bridged binuclear Cu(II) complex {(pmtpm)Cu}2(μ-Cl)2](ClO4)2 (3) derived from a tridentate Schiff base ligand, 2-pyridyl-N-(2′-methylthiophenyl)methyleneimine (pmtpm) were synthesized and characterized by various spectroscopic methods and by X-ray crystallography. (N2S)CuCl2 chromophore(s) of distorted square pyramidal coordination geometries around Cu(II) ion(s) have been observed for all the complexes 1-3. The equatorial sites of the square plane comprise two N and a thioether S donor atoms of the pmtpm ligand as well as one Cl− ion (terminal in 1 and 2, and bridging in 3) while the remaining axial site is occupied by a terminal Cl− ion (for 1) or a bridging Cl− ion (for 2 and 3). The equatorial Cu-Cl distances are much shorter 1: 2.2511(4) Å, 2: 2.2307(12) Å, 3: 2.2513(12) Å] than the axial Cu-Cl distances 1: 2.4394(4) Å, 2: 2.5597(9) Å, 3: 2.7037(12) Å]. The correlation of an axial Cu-Cl bond elongation with a lower g|| value in the solid state EPR spectrum and a blue shifted ligand field transition in the solid and solution phase absorption spectrum has been observed. |
| |
| Keywords: | Mono-μ-chloro and di-μ-chloro bridged binuclear copper(II) complexes Tridentate Schiff&rsquo s base ligand N S donor ligand Jahn-Teller distortion |
| 本文献已被 ScienceDirect 等数据库收录！ |
|
