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Binuclear CuII complexes having new flexible heptadentate ligands 2,6-bis{[bis(3,3′-N,N-dimethylaminopropyl)amino]methyl}-4-bromophenol [HL1], 2,6-bis(3,3′-N,N-dimethylaminopropyl)amino]methyl}-4-methylphenol [HL2], and 2,6-bis{[bis(3,3′-N,N-dimethylaminopropyl)amino]methyl}-4-methoxyphenol [HL3], capable of assembling two copper ions in close proximity have been synthesized. Comparisons of the charge-transfer (CT) features, observed in electronic spectra of these complexes, are correlated with the electronic effect on the aromatic ring of the ligand systems. Cyclic voltammetry has revealed the existence of two reduction couples, $${\text{Cu}}^{{\text{II}}} {\text{Cu}}^{{\text{II}}} \rightleftharpoons {\text{Cu}}^{{\text{II}}} {\text{Cu}}^{\text{I}} \rightleftharpoons {\text{Cu}}^{\text{I}} {\text{Cu}}^{\text{I}}$$ The first is sensitive to the electronic effects of aromatic ring substituents of the ligand system, shifting to more positive potentials when more electrophilic groups replace the existing substituents. The conproportionation constants (kcon) for the mixed valent CuICuII complexes have been determined electrochemically. The magnetic susceptibilities of the complexes have been measured over the 70–300 K range and the exchange coupling parameter (−2J) determined by a least squares fit of the data which indicates an antiferromagnetic spin exchange (−2J = 94–172 cm−1) between the CuII ions with bridging units in the order: N3 ≈ NO2 > OAc > OH. |
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