Twot rinuclearc opper phosphonate complexes, [Cu 3 (pda) 3 (tBuPO 3 )]·2(Et 3 NH) (1)a nd [Cu 3 (pda) 3 (PhPO 3 )]· 2(Et 3 NH) (2), have been synthesized and investigated by a combination of X-ray crystallography,P XRD, magneto-and electrochemistry,E PR,i ns itu UV-vis spectroelectrochemistry and DLS.T he two complexes feature almosti denticalc rystal structures,t he anions of which are both supported by pda 2À and tBuPO 3 2À /PhPO 3 2À groups, bridging threef ive-coordinated Cu II atoms to form ac rown-like structure. Thisi st he first time that trinuclearc opper 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.T he electrocatalytic activity for water oxidation of the two complexes was preliminarilyi nvestigated, which reveals that both of the two complexes can carry out electrocatalytic water oxidationi naneutral system owing to the introduction of phosphonate ligands into the complexes, with aT OF of about 0.82 s À1 (1)a nd 0.58 s À1 (2), respectively.W e propose that the presence of phosphonatel igands may affect the magnetic property and catalytic activity of the complexes.[a] J.
A bio-inspired cubane-like tetranuclear cluster [Cu4(pdmH)4(OAc)2](NO3)2·3H2O can electrocatalyze water oxidation under aqueous alkaline conditions through a PCET process.
The electrochemical properties of two complexes, [RuII(η3‐(N,N,N)‐OMePDI)Cl2(PPh3)]0 (1) and [RuII(η2‐(C,N)‐OMePDI‐H)Cl (PPh3)2]0 (2), were studied. In octahedral complex 1, bis(imino)pyridine (PDI) is a tridentate η3‐N,N,N‐coordinated ligand, whereas in trigonal‐bipyramidal complex 2, the deprotonated PDI ligand adopts the unusual bidentate binding mode η2‐C,N to coordinate to the central Ru(II) ion. Bulk electrolysis in two electrolyte solutions of acetonitrile (MeCN) and tetrahydrofuran (THF) suggests that complexes 1 and 2 have very different electrocatalytic CO2 reduction activities. In MeCN solution, complex 1 can selectively electrocatalytic CO2 reduction to CO with a Faradaic efficiency of about 50% and a turnover frequency (TOF) of 4.4 s−1, whereas complex 2 can perform electrocatalytic of CO2 reduction with a Faraday efficiency of ~22% and a TOF of 0.3 S−1. The electrocatalytic CO2 reduction selectivity and activity of the two complexes are poor when the solvent is changed to THF. Combined with the results of the density functional theory calculation, we propose that the binding pattern of the redox‐active ligand OMePDI has a significant effect on the electrocatalytic activity for the two Ru(II)PDI complexes.
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