Synthesis, properties and surface self-assembly of a pentanuclear cluster based on the new π-conjugated TTF-triazole ligand

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 Cu(II) cluster (Cu(5)(tta)(4)(TTFN(3))(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.