Park Jihye, Hinckley Allison C, Huang Zhehao, Feng Dawei, Yakovenko Andrey A, Lee Minah, Chen Shucheng, Zou Xiaodong, Bao Zhenan
Department of Chemical Engineering , Stanford University , Stanford , California 94305 , United States.
Berzelii Centre EXSELENT on Porous Materials, Department of Materials and Environmental Chemistry , Stockholm University , SE-106 91 Stockholm , Sweden.
J Am Chem Soc. 2018 Nov 7;140(44):14533-14537. doi: 10.1021/jacs.8b06666. Epub 2018 Oct 30.
Conductive metal-organic frameworks (c-MOFs) have shown outstanding performance in energy storage and electrocatalysis. Varying the bridging metal species and the coordinating atom are versatile approaches to tune their intrinsic electronic properties in c-MOFs. Herein we report the first synthesis of the oxygen analog of M(CX) (X = NH, S) family using Cu(II) and hexahydroxybenzene (HHB), namely Cu-HHB [Cu(CO)], through a kinetically controlled approach with a competing coordination reagent. We also successfully demonstrate an economical synthetic approach using tetrahydroxyquinone as the starting material. Cu-HHB was found to have a partially eclipsed packing between adjacent 2D layers and a bandgap of approximately 1 eV. The addition of Cu-HHB to the family of synthetically realized M(CX) c-MOFs will enable greater understanding of the influence of the organic linkers and metals, and further broadens the range of applications for these materials.
导电金属有机框架（c-MOFs）在能量存储和电催化方面表现出卓越性能。改变桥连金属物种和配位原子是调节c-MOFs内在电子性质的通用方法。在此，我们报告了通过一种动力学控制方法并使用竞争配位试剂，首次合成了M(CX)（X = NH，S）家族的氧类似物，即Cu-HHB [Cu(CO)]，使用的是Cu(II)和六羟基苯（HHB）。我们还成功展示了一种以四羟基醌为起始原料的经济合成方法。发现Cu-HHB在相邻二维层之间具有部分重叠堆积，带隙约为1 eV。将Cu-HHB添加到合成实现的M(CX) c-MOFs家族中，将有助于更深入了解有机连接体和金属的影响，并进一步拓宽这些材料的应用范围。
