Synthesis, Structure, and Properties of Al(Rbpy)3 Complexes (R = t-Bu, Me): Homoleptic Main-Group Tris-bipyridyl Compounds

详细信息    查看全文

• 作者：Samantha DeCarlo ; Dennis H. Mayo ; Warren Tomlinson ; Junkai Hu ; Joseph Hooper ; Peter Zavalij ; Kit Bowen ; Hansgeorg Schnöckel ; Bryan Eichhorn
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：May 2, 2016
• 年：2016
• 卷：55
• 期：9
• 页码：4344-4353
• 全文大小：563K
• 年卷期：0
• ISSN：1520-510X

文摘

The neutral homoleptic tris-bpy aluminum complexes Al(^Rbpy)₃, where R = tBu (1) or Me (2), have been synthesized from reactions between AlX precursors (X = Cl, Br) and neutral ^Rbpy ligands through an aluminum disproportion process. The crystalline compounds have been characterized by single-crystal X-ray diffraction, electrochemical experiments, EPR, magnetic susceptibility, and density functional theory (DFT) studies. The collective data show that 1 and 2 contain Al³⁺ metal centers coordinated by three bipyridine (bpy^•)^1– monoanion radicals. Electrochemical studies show that six redox states are accessible from the neutral complexes, three oxidative and three reductive, that involve oxidation or reduction of the coordinated bpy ligands to give neutral ^Rbpy or ^Rbpy^2– dianions, respectively. Magnetic susceptibility measurements (4–300 K) coupled with DFT studies show strong antiferromagnetic coupling of the three unpaired electrons located on the ^Rbpy ligands to give S = ¹/₂ ground states with low lying S = ³/₂ excited states that are populated above 110 K (1) and 80 K (2) in the solid-state. Complex 2 shows weak 3D magnetic interactions at 19 K, which is not observed in 1 or the related [Al(bpy)₃] complex.