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Structures and spectroscopic properties of chain polymeric complexes of copper(II) halides with 2,3,5,6-tetrafluoro-1,4-bis(2-pyridylsulfenyl)benzene and its 4-pyridylsulfenyl analogue
journal contribution
posted on 2023-05-16, 11:14 authored by Goodgame, ML, Grachvogel, DA, Hitchman, MA, Long, NJ, Stratemeier, H, White, AJP, Wicks, JLM, Williams, DJThe syntheses are reported of the "extended reach" ligand 2,3,5,6-tetrafluoro-1,4-bis(2-pyridylsulfenyl)benzene (L1), its 4-pyridylsulfenyl analogue (L2), and their copper(II) complexes CuLX2 (X = Cl or Br). X-ray studio have been carried out on L1, L2, and the complexes Cu(L1)Cl2·2CHCl3 (1) and [Cu(L2)(DMF)Br2]·DMF (2). Complex 1 has a chain polymeric structure with a trans-planar CuCl2N2 coordination geometry. Complex 2 is also a chain polymer structure, but in this case a DMF molecule is bonded in the apical position above a trans-CuBr2N2 unit, producing a slightly distorted square pyramidal geometry at the copper centers. The transition energies obtained from the single-crystal electronic spectrum of Cu(L1)Cl2·2CHCl3 and the g-values from its EPR spectrum are used to derive bonding parameters, and these are compared with those of other planar CuL2Cl2 complexes with amine ligands. The electronic reflectance spectrum of [Cu(L2)(DMF)Br2]·DMF implies broadly similar amine bonding parameters. This compound exhibits an unusual g-tensor with g∥ < g⊥, which is interpreted in terms of exchange-averaging of the molecular g-tensors of the two molecules in the unit cell.
History
Publication title
Inorganic ChemistryVolume
37Issue
24Pagination
6354-6360ISSN
0020-1669Department/School
School of Natural SciencesPublisher
American Chemical SocietyPlace of publication
Washington D.C., USARepository Status
- Restricted