Stepwise Assembly of M Clusters Revealed by Mass Spectrometry, EXAFS, and Crystallography.

The square-planar monomer NiL (Ni ), L=2-ethoxy-6-(N-methyl-iminomethyl)phenolate, reacts with M(H O) (ClO ) , M=Ni or Co, to form heptanuclear disks Co Ni (OH) (L) ⋅2 CH CN (Co Ni , x=0-7) and the co-crystal [Co Ni (OH) L ]NiL ⋅2 CH CN (Co Ni -Ni ) under ambient conditions. It has proved possible to explore the bottom-up assembly process of Co Ni and Co Ni -Ni in real time. The final products have been characterized by thermogravimetric analysis, IR, elemental analysis, ICP-MS, and single-crystal X-ray diffraction. Time-dependent mass spectrometry (MS) revealed the following reaction steps: Ni →[M L ] →[M (OH) L ] →[M (OH) L ] . In contrast, the reaction of Ni with Zn only reaches halfway, and crystallographic evidence indicates a butterfly structure for [Zn Ni (OH) Cl ] (Zn Ni ), an intermediate that is difficult to isolate in the above Ni-Co series. A summation method has been used to analyze the MS of bimetallic clusters with very similar atomic masses, as is the case for Co and Ni. The results provide ample information on the distribution of Co and Ni within each cluster and their statistical distribution within selected crystals.