Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes)-UMR 6226, 35000, Rennes, France.
Chemistry. 2020 Jul 8;26(38):8368-8371. doi: 10.1002/chem.202000910. Epub 2020 Jun 10.
The unprecedented tetrairon dication {Cp*(dppe)FeC≡C-} -μ-(1,2,4,5-C H ) (1) was obtained through a sequence of three reactions from 1,2,4,5-tetraethynylbenzene, Cp*(dppe)FeCl (Cp*=C Me , dppe=1,2-bis(diphenylphosphino)-ethane), KOtBu, and ferrocenium hexafluorophosphate. The cyclic voltammogram of the target molecule, isolated in 77 % yield, exhibits four well separated and reversible redox events showing that 1 is thermodynamically stable with respect to disproportionation (Kc>10 ). The tetranuclear dication 1 was characterized by XRD on single crystal, IR and NMR spectroscopies and Mössbauer spectrometry. The experimental data show that 1 behaves as a class II mixed-valence complex with the positive charges preferentially disposed on antipodal positions. This new molecule can be regarded as a potential molecular prototype of quantum dot cellular automata.
通过一系列三步反应，从 1,2,4,5-四乙炔基苯、Cp*(dppe)FeCl（Cp*=CMe ，dppe=1,2-双（二苯基膦）乙烷）、KOtBu 和六氟磷酸铁得到了前所未有的四铁二价阳离子[{Cp*(dppe)FeC≡C-} -μ-(1,2,4,5-CH)]（PF ）（1）。目标分子的循环伏安图在 77%的产率下分离出来，表现出四个很好的分离和可逆的氧化还原事件，表明 1 相对于歧化反应是热力学稳定的（Kc>10）。四核二价阳离子 1 通过单晶 XRD、IR 和 NMR 光谱以及穆斯堡尔谱进行了表征。实验数据表明，1 表现为类 II 混合价络合物，正电荷优先占据对映位置。这个新分子可以被看作是量子点细胞自动机的潜在分子原型。
