Structural and electrochemical properties of mononuclear copper(II) complexes with pentadentate ethylenediamine-based ligands with pyridine/quinoline/isoquinoline/quinoxaline binding sites.

N-Monosubstituted ethylenediamine derivatives with three methylene-tethered aromatic groups ((ArCH2)2NCH2CH2N(R)CH2Ar (R-ArArAr), where Ar = 2-pyridyl, 2-quinolyl, 1- and 3-isoquinolyl and 2-quinoxalyl; R = methyl, benzyl and phenyl) were utilized as pentadentate ligands for copper(II) complexation. Fifteen mononuclear copper(II) complexes were synthesized and exhibit differences in cyclic voltammetry, absorption spectroscopy and solid state geometries, depending on the aromatic group (Ar) and the substituent on the aliphatic nitrogen atom (R) of the ligand. Compared with the pyridine and isoquinoline complexes, the quinoline and quinoxaline derivatives exhibit distinct Cu(II)/Cu(I) redox potentials and d–d transition absorption wavelengths. Similarly, the phenyl derivatives are different from their methyl and benzyl counterparts. These characteristic trends are discussed in relation to the square-pyramidal/trigonal–bipyramidal structure of the complexes which is perturbed by the location of quinoline moieties in the penta- or hexacoordinate complexes with Jahn–Teller distortion. In addition, the results are compared to the copper(II) complexes with pyridine/quinoline mixed ligands, Ph-Ar1Ar2Ar3 ((Ar1CH2)(Ar2CH2)NCH2CH2N(Ph)CH2Ar3). [ABSTRACT FROM AUTHOR]