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Two Trinuclear Cu II Complexes: Effect of Phosphonate Ligand on the Magnetic Property and Electrocatalytic Reactivity for Water Oxidation
Author(s) -
Wang JinMiao,
Liu YaRong,
Mao XueYang,
Shi NingNing,
Zhang Xia,
Wang HuiSheng,
Fan YuHua,
Wang Mei
Publication year - 2019
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201900531
Subject(s) - phosphonate , chemistry , crystallography , electrochemistry , ligand (biochemistry) , copper , reactivity (psychology) , inorganic chemistry , electron paramagnetic resonance , metal , magnetic susceptibility , catalysis , crystal structure , electrode , organic chemistry , nuclear magnetic resonance , medicine , biochemistry , physics , receptor , alternative medicine , pathology
Two trinuclear copper phosphonate complexes, [Cu 3 (pda) 3 ( t BuPO 3 )]⋅2(Et 3 NH) ( 1 ) and [Cu 3 (pda) 3 (PhPO 3 )]⋅2(Et 3 NH) ( 2 ), have been synthesized and investigated by a combination of X‐ray crystallography, PXRD, magneto‐ and electrochemistry, EPR, in situ UV‐vis spectroelectrochemistry and DLS. The two complexes feature almost identical crystal structures, the anions of which are both supported by pda 2− and t BuPO 3 2− /PhPO 3 2− groups, bridging three five‐coordinated Cu II atoms to form a crown‐like structure. This is the first time that trinuclear copper phosphonate complexes have been isolated and characterized. Magnetic susceptibility measurements reveal that complexes 1 and 2 both display overall ferromagnetic characters, but with different exchange interactions between the metal ions within the two clusters. The electrocatalytic activity for water oxidation of the two complexes was preliminarily investigated, which reveals that both of the two complexes can carry out electrocatalytic water oxidation in a neutral system owing to the introduction of phosphonate ligands into the complexes, with a TOF of about 0.82 s −1 ( 1 ) and 0.58 s −1 ( 2 ), respectively. We propose that the presence of phosphonate ligands may affect the magnetic property and catalytic activity of the complexes.