The syntheses are reported of the "extended reach" Ligand 2,3,5,6-tetrafluoro-1,4-bis(2-pyridylsulfenyl)benzene, (L-1), its 4-pyridylsulfenyl analogue (L-2), and their copper(II) complexes CuLX2 (X = Cl or Br). X-ray studies have been carried out on L-1, L-2, and the complexes Cu(L-1)Cl-2. 2CHCl(3) (1) and [Cu(L-2)(DMF)Br-2]. 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 transs-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(L-1)Cl-2. 2CHCl(3) 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(L-2)(DMF)Br-2]. DMF implies broadly similar amine bonding parameters. This compound exhibits an unusual g-tensor with g(parallel to) < g(perpendicular to), which is interpreted in terms of exchange-averaging of the molecular g-tensors of the two molecules in the unit cell.