Rhenium(I) Tricarbonyl Complexes with New Pyridine Ligands Containing Crown Ether-Annelated or Anthracene-Functionalized 1,3-Dithiole-2-ylidene

Two bispyridine ligands containing crown ether-annelated or anthryl-substituted 1,3-dithiole-2-ylidene, 4,5-dithia-(3′,6′,9′,12′-tetraoxatetradecyl)-2-bis(2-pyridyl)methylene-1,3-dithiole (BPyDT(O4S2), 3) and 4-methylthio-5-[{2-(9′-anthryloxy)-ethyl}thio]-2-bis(2-pyridyl)methylene-1,3-dithiole (BPyDT(SMe)(SEA), 7), have been synthesized and characterized. The rhenium(I) tricarbonyl complexes ClRe(CO)3(BPyDT(O4S2)) (4) and BrRe(CO)3(BPyDT(SMe)(SEA)) (8) have been prepared based on them. The crystal structures of compounds 3, 4, and 8 have been determined. Complexes 4 and 8 exhibit greenish-yellow emission, while ligands 3 and 7 show blue luminescence in fluid solutions at room temperature. Redox properties of 3, 4, 7, and 8 have been investigated by cyclic voltammetry, and the crown ether-annelated compounds 3 and 4 show significant Na+-binding properties with large positive redox shifts.

本研究合成并表征了两种含冠醚稠合或蒽基取代1,3-二硫杂环戊烯-2-亚基的双吡啶配体，即4,5-二硫杂-(3′,6′,9′,12′-四氧杂十四烷基)-双(2-吡啶基)亚甲基-1,3-二硫杂环戊烷（BPyDT(O4S2)，3）与4-甲硫基-5-[{2-(9′-蒽氧基)乙基}硫基]-双(2-吡啶基)亚甲基-1,3-二硫杂环戊烷（BPyDT(SMe)(SEA)，7）。基于上述配体，成功制备了铼(I)三羰基配合物ClRe(CO)3(BPyDT(O4S2))（4）与BrRe(CO)3(BPyDT(SMe)(SEA))（8）。现已解析得到化合物3、4及8的晶体结构。在室温液态溶液中，配合物4与8呈现绿黄色发射，而配体3与7则展现出蓝色发光性能。通过循环伏安法对3、4、7及8的氧化还原性质进行了研究，其中冠醚稠合的化合物3与4表现出显著的Na+结合特性，并伴随较大的正氧化还原位移。