Three copper complex borates, [Cu(en) 2 ]·[B 4 O 5 (OH) 4 ]·2H 3 BO 3 ( 1 , en = ethylenediamine), [Cu(Eten) 2 ]·[B 5 O 6 (OH) 4 ] 2 ( 2 , Eten = N -ethyl ethylenediamine) and [Cu(Dmen) 2 ]·[B 10 O 13 (OH) 6 ] ( 3, Dmen = N,N -dimethyl ethylenediamine) have been successfully synthesized and structurally characterized by single-crystal X-ray diffraction, PXRD, and FTIR. Their oxoboron clusters are [B 4 O 5 (OH) 4 ] 2− , [B 5 O 6 (OH) 4 ] − and [B 10 O 13 (OH) 6 ] 2− , respectively. Copper ion was used as the central atom, ethylenediamine and its derivatives were selected as ligand. The structure of oxoboron clusters in 1 , 2 and 3 can be modulated through varying ethylenediamine derivative ligand, as well as temperature and pressure of reaction system. These copper complex borates exhibited open framework formed by the interconnection of hydrogen bonds of oxoboron clusters. Moreover, the oxygen reduction reaction activity of these borate-based catalysts was investigated. The half-wave potential values of the products after heating 1 – 3 with carbon at 600 °C (1/C-600, 2/C-600 and 3/C-600) were 0.817, 0.80 and 0.73 V, respectively.
Two imidazole-based ligand-nickel borates, [Ni(1-ipIM) 3 ·B 6 O 7 (OH) 6 ]·[H 3 BO 3 ]·2·.5H 2 O ( 1 , 1-ipIM = 1-isopropylimidazole) and [Ni(1-pIM) 6 ]·[B 5 O 6 (OH) 4 ]·2H 2 O ( 2 , 1-pIM = 1-propylimidazole) have been synthesized and structurally characterized by single-crystal X-ray diffraction, PXRD, FTIR. The oxoboron cluster structures of 1 and 2 were modulated through changing the carbon-branched structure on the N -site of the imidazole-based ligand using metallic nickel as the central atom. It is noteworthy that the structure of 1 is a hybridized skeleton formed by N -Ni-O-B bonds. The electrocatalytic oxygen reduction reaction (ORR) activity of these borate-based catalysts was investigated. The half-wave potential ( E 1/2 ) values of 1 -based and 2 -based were about 0.825 and 0.80 V, respectively.
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