Abstract
The new π-extended redox-active ligand with both TTF and triazole units, 6-(4,5-bis(propylthio)-1,3-dithiol-2-ylidene)-1H-[1,3]dithiolo[4′,5′:4,5]benzo [1,2-d] [1–3]triazole, has been successfully prepared. Based on the versatile ligand and Cu(tta)2 precursors (tta− = 4,4,4-trifluoro-1-(thiophen-2-yl)butane-1,3-dione), a TTF-based pentanuclear CuII cluster (Cu5(tta)4(TTFN3)6) is synthesized and structurally characterized. Their absorption and electrochemical properties are investigated. Antiferromagnetic couplings are operative between metal ion centers bridged by triazoles in the complex. The self-assembled structure of the cluster complex on a highly oriented pyrolytic graphite (HOPG) surface was observed using scanning tunneling microscopy and density functional theory (DFT) calculations have been performed to provide insight into the formation mechanism. The introduction of the redox-active TTF unit into the cluster complexes with interesting magnetic properties renders them promising candidates for new multifunctional materials.
Highlights
Avarvari and co-workers reported a new TTF-triazole ligand with 1-substituted benzyl (TTF moieties are linked to the triazole through an C-C single bond) and its CuII complex[34]
To further enhance the interaction of conducting and magnetic π -d systems, it is important to shorten the distance between the magnetic metal ion and the conducting TTF units by designing new π -conjugated ligands
Cyclic and square wave voltammetry measurements on the compound L revealed two reversible one-electron oxidation processes at E1/2 = 0.175 and 0.575 V vs. ferrocenium/ ferrocene couple (Fc+/Fc) (Figs S4 and S5, SI) which can be attributed to the oxidation of the neutral TTF core to its radical cation species, followed by a further oxidation to its dication state, respectively
Summary
Cyclic and square wave voltammetry measurements on the compound L revealed two reversible one-electron oxidation processes at E1/2 = 0.175 and 0.575 V vs Fc+/Fc (Figs S4 and S5, SI) which can be attributed to the oxidation of the neutral TTF core to its radical cation species, followed by a further oxidation to its dication state, respectively These two oxidation processes persist in complex 1, and occur at similar E1/2 values of 0.176 and 0.592 V. It is interesting that on the HOPG surface, we only observed the regular assembly formed by quadrangles This result implies that on the surface, each CuII is coordinated to four TTFN3 ligands.
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