Wang Jin-Miao, Liu Ya-Rong, Mao Xue-Yang, Shi Ning-Ning, Zhang Xia, Wang Hui-Sheng, Fan Yu-Hua, Wang Mei
Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, Shandong, 266100, P. R. China.
Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan, 430074, P. R. China.
Chem Asian J. 2019 Aug 1;14(15):2685-2693. doi: 10.1002/asia.201900531. Epub 2019 Jul 1.
Two trinuclear copper phosphonate complexes, [Cu (pda) (tBuPO )]⋅2(Et NH) (1) and [Cu (pda) (PhPO )]⋅2(Et 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 and tBuPO /PhPO groups, bridging three five-coordinated Cu 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) and 0.58 s (2), respectively. We propose that the presence of phosphonate ligands may affect the magnetic property and catalytic activity of the complexes.
通过X射线晶体学、粉末X射线衍射、磁学和电化学、电子顺磁共振、原位紫外可见光谱电化学以及动态光散射等方法相结合，合成并研究了两种三核铜膦酸盐配合物，即[Cu (pda) (tBuPO )]⋅2(Et NH) (1)和[Cu (pda) (PhPO )]⋅2(Et NH) (2)。这两种配合物具有几乎相同的晶体结构，其阴离子均由pda和tBuPO /PhPO 基团支撑，桥连三个五配位的铜原子形成冠状结构。这是首次分离并表征三核铜膦酸盐配合物。磁化率测量表明，配合物1和2均表现出整体铁磁特性，但两个簇内金属离子之间的交换相互作用不同。初步研究了这两种配合物对水氧化的电催化活性，结果表明，由于配合物中引入了膦酸盐配体，两种配合物在中性体系中均能进行电催化水氧化，其转换频率分别约为0.82 s (1)和0.58 s (2)。我们认为，膦酸盐配体的存在可能会影响配合物的磁性和催化活性。
