Premium
Stepwise Assembly of M II 7 Clusters Revealed by Mass Spectrometry, EXAFS, and Crystallography
Author(s) -
Na HongXu,
Yang PeiYu,
Yin Zheng,
Wang YunHong,
Chang LiXian,
Si Rui,
Kurmoo Mohamedally,
Zeng MingHua
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201603652
Subject(s) - bimetallic strip , thermogravimetric analysis , crystallography , chemistry , crystal structure , mass spectrometry , single crystal , cluster (spacecraft) , x ray crystallography , extended x ray absorption fine structure , analytical chemistry (journal) , diffraction , catalysis , absorption spectroscopy , physics , organic chemistry , optics , chromatography , quantum mechanics , computer science , programming language , biochemistry
The square‐planar monomer NiL 2 ( Ni 1 ), L=2‐ethoxy‐6‐( N ‐methyl‐iminomethyl)phenolate, reacts with M(H 2 O) 6 (ClO 4 ) 2 , M=Ni or Co, to form heptanuclear disks [Co x Ni 7− x (OH) 6 (L) 6 ](ClO 4 ) 2 ⋅ 2 CH 3 CN ( Co x Ni 7− x , x =0–7) and the co‐crystal [Co x Ni 7− x (OH) 6 L 6 ][NiL 2 ](ClO 4 ) 2 ⋅ 2 CH 3 CN ( Co x Ni 7− x ‐Ni 1 ) under ambient conditions. It has proved possible to explore the bottom‐up assembly process of Co x Ni 7− x and Co x Ni 7− x ‐Ni 1 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 1 →[M 2 L 3 ] + →[M 4 (OH) 2 L 4 ] 2+ →[M 7 (OH) 6 L 6 ] 2+ . In contrast, the reaction of Ni 1 with Zn 2+ only reaches halfway, and crystallographic evidence indicates a butterfly structure for [Zn 2 Ni 2 (OH) 2 Cl 2 ] ( Zn 2 Ni 2 ), 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.