Anion exchange coupled with the reduction and dimerisation of a copper(ii) nitrate complex of tripyridyl dithioether via a single-crystal-to-single-crystal transformation

Autor: In-Hyeok Park, Hyeong-Hwan Lee, Shim Sung Lee, Huiyeong Ju, Seulgi Kim, Mari Ikeda, Jong Hwa Jung, Yoichi Habata, Eunji Lee
Rok vydání: 2017
Předmět:
Zdroj: Chemical Science. 8:2592-2596
ISSN: 2041-6539
2041-6520
DOI: 10.1039/c6sc05341f
Popis: It is a challenge to develop methodologies involving multiple transformations for preparing new materials that cannot be obtained via direct synthesis. Herein, we report an anion exchange process accompanying cation reduction and dimerisation via a single-crystal-to-single-crystal transformation. First, a direct reaction of the flexible tripyridyl dithioether ligand L with CuI afforded a mixture of four bis(ligand) complexes (1a-1d). To avoid the formation of undesired mixed products, a copper(ii) nitrate complex-mediated approach involving anion exchange and cation reduction was employed to generate a monomeric complex, [CuII(L)NO3]NO3·toluene (2). When the dark blue crystals of 2 were immersed in an aqueous NaI solution, the crystals were transformed to a pale yellow dimeric copper(i) iodide complex, [(μ-CuI2I2)(L)2] (3). The observed anion exchange promotes the reduction of copper(ii) to copper(i) at the expense of I-/I3- oxidation as well as dimerisation via the formation of a Cu2I2 cluster. This result corresponds to the synthesis of a compound that otherwise was not able to be prepared via a direct synthetic procedure.
Databáze: OpenAIRE