Abstract
A metal-free 16-membered N4-donor [1 + 1] Schiff-base macrocycle was isolated as HL(Pr)·2acid, by 1 : 1 condensation of diphenylamine-2,2'-dicarboxaldehyde (1), dipropylene triamine and an excess of either acetic or formic acid, or as HL(Pr)·(tosylic acid) when just one equivalent of tosylic acid was employed. Interestingly, the acid-free synthesis employed for the 14-membered analogue HL(Et) failed to generate pure HL(Pr) macrocycle, but nevertheless the crude product obtained was able to be used in subsequent complexation reactions to form five mononuclear complexes: Zn(II)L(Pr)(BF4)·H2O·0.5IPA (where IPA is isopropylalcohol), [Cu(II)L(Pr)](BF4), [Ni(II)L(Pr)](BF4), [Co(II)L(Pr)](BF4)·0.5H2O, [Fe(III)L(Pr)(NCS)2]·1.5H2O. Crystal structure determinations show that, like the HL(Et) analogues, [Ni(II)L(Pr)](BF4) features a square planar N4 coordinated Ni(II) centre and [Fe(III)L(Pr)(NCS)2]·0.15MeOH·0.2H2O features an octahedral N6 coordinated Fe(III) centre (two NCS anions bound axially). In both cases the N4-donor macrocycle is bound equatorially to the metal ion. Cyclic voltammograms of the BF4 complexes were carried out in MeCN vs. 0.01 mol L(-1) AgNO3/Ag and revealed multiple redox processes. The Zn(II) complex exhibits multiple ligand-centered redox processes. Interestingly, [Ni(II)L(Pr)](BF4) has two reversible redox processes, at E(m) = +0.38 (ΔE = 0.06 V) and -1.7 V (ΔE = 0.06 V), whereas the previously reported analogue [Ni(II)L(Et)](BF4) had a process at E(pc) = +0.59 V with only a weak return wave. Likewise, [Cu(II)L(Pr)](BF4) has a reversible process, at E(m) = -1.17 V (ΔE = 0.06 V) plus a process at E(pc) = +0.45 V, whereas previously reported [Cu(II)L(Et)](BF4) only featured irreversible processes, with the oxidation occurring at E(pc) = +0.50 V.