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Overcoming Statistical Complexity: Selective Coordination of Three Different Metal Ions to a Ligand with Three Different Coordination Sites
Author(s) -
Akine Shigehisa,
Matsumoto Takashi,
Nabeshima Tatsuya
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201508065
Subject(s) - coordination number , ligand (biochemistry) , metal ions in aqueous solution , metal , chemistry , coordination complex , ion , cluster (spacecraft) , molecule , computational chemistry , computer science , organic chemistry , biochemistry , receptor , programming language
In general, it is difficult to selectively introduce different metal ions at specific positions of a cluster‐like structure. This is mainly due to statistical problems as well as the reversibility of the formation of coordination bonds. To overcome this statistical problem, we used a carefully designed ligand, H 6 L, which can accommodate three different kinds of metal ions in three types of coordination sites. The complex [LNiZn 2 La] 3+ , which contains three different metals, was quantitatively obtained by a stepwise procedure, but different products were obtained when the metal ions were added in a different order. However, equilibration studies indicated that this complex was almost solely formed among 54 (=3×3× 3 H 2 ) possible products upon heating; the formation efficiency (ca. 100 %) was significantly higher than the statistical probability (2.47 %). Such carefully designed ligands should be useful for the synthesis multimetallic systems, which are of interest because of the interplay between the different metals.