State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210093, P.R. China.
CAS Key Laboratory of Standardization and Measurement for Nanotechnology, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, 100190, P.R. China.
Sci Rep. 2016 May 6;6:25544. doi: 10.1038/srep25544.
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 (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.
新型π扩展氧化还原活性配体，同时具有 TTF 和三唑单元，6-(4,5-双(丙硫基)-1,3-二硫杂-2-亚基)-1H-[1,3]二硫杂环戊烯并[4',5':4,5]苯并[1,2-d][1-3]三唑，已经成功制备。基于多功能配体和 Cu(tta)2 前体（tta(-)=4,4,4-三氟-1-(噻吩-2-基)丁烷-1,3-二酮），合成并结构表征了一种基于 TTF 的五核 Cu(II)簇（Cu5(tta)4(TTFN3)6）。研究了它们的吸收和电化学性质。在配合物中，通过三唑桥连的金属离子中心之间存在反铁磁耦合。使用扫描隧道显微镜观察了簇配合物在高度取向的热解石墨（HOPG）表面上的自组装结构，并进行了密度泛函理论（DFT）计算，以深入了解形成机制。将氧化还原活性的 TTF 单元引入具有有趣磁性的簇配合物中，使它们成为新型多功能材料的有前途的候选物。
