The reactions between 4′-phenyl-terpyridine (L) and nitrate, acetate or chloride Cu(II) salts led to the formation of [Cu(NO₃)₂L] (1), [Cu(OCOCH₃)₂L]·CH₂Cl₂ (2·CH₂Cl₂) and [CuCl₂L]·[Cu(Cl)(μ-Cl)L]₂ (3), respectively. Upon dissolving 1 in mixtures of DMSO–MeOH or EtOH–DMF the compounds [Cu(H₂O){OS(CH₃)₂}L](NO₃)₂ (4) and [Cu(HO)(CH₃CH₂OH)L](NO₃) (5) were obtained, in this order. Reaction of 3 with AgSO₃CF₃ led to [CuCl(OSO₂CF₃)L] (6). The compounds were characterized by ESI-MS, IR, elemental analysis, electrochemical techniques and, for 2–6, also by single crystal X-ray diffraction. They undergo, by cyclic voltammetry, two single-electron irreversible reductions assigned to Cu(II) → Cu(I) and Cu(I) → Cu(0) and, for those of the same structural type, the reduction potential appears to correlate with the summation of the values of the Lever electrochemical E_L ligand parameter, which is reported for the first time for copper complexes. Complexes 1–6 in combination with TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl radical) can exhibit a high catalytic activity, under mild conditions and in alkaline aqueous solution, for the aerobic oxidation of benzylic alcohols. Molar yields up to 94% (based on the alcohol) with TON values up to 320 were achieved after 22 h.

Reactions between 4′-phenyl-terpyridine (L) and several Zn(II) salts (trifluoromethane sulfonate, p-toluenesulfonate, benzoate, p-hydroxybenzoate, o-hydroxybenzoate or m-hydroxybenzoate) led to the formation of the complexes [Zn(OSO₂CF₃)₂L(H₂O)] (1), [Zn(p-OSO₂PhCH₃)₂L] (2), [Zn(OCOPh)₂L] (3), [Zn(p-OCOPhOH)₂L] (4), [Zn(o-OCOPhOH)₂L] (5) and [Zn(m-OCOPhOH)₂L] (6), which were characterized by elemental analysis, ¹H NMR, ¹³C NMR, IR, single crystal X-ray diffraction and fluorescence spectroscopies. In 1, the Zn atom is hexacoordinated, with a N₃O₃ coordination environment, whereas in the remaining structures the metal atom is envisaged as possessing distorted N₃O₂ irregular trigonal bipyramidal coordination geometries. All the compounds show interesting photo-luminescent properties in solid and solution states in DMF, DMSO and methanol, which are reported along with their TG-DTA thermal decomposition processes.