Chen Chao-Long, Wang Cong, Zheng Xiu-Ying, Zhang Ruihua, Xu Yiling, Zhuang Gui-Lin, Long La-Sheng, Zheng Lan-Sun, Kong Xiang-Jian, Cao Yang
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China.
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, People's Republic of China.
J Am Chem Soc. 2023 Aug 9;145(31):16983-16987. doi: 10.1021/jacs.3c05336. Epub 2023 Jul 28.
Electrically conductive metal-organic frameworks (MOFs) have been extensively studied for their potential uses in energy-related technologies and sensors. However, achieving that goal requires MOFs to be highly stable and maintain their conductivity under practical operating conditions with varying solution environments and temperatures. Herein, we have designed and synthesized a new series of {Ln(μ-O)(μ-OH)(INA)(GA)(HO)} (denoted as , Ln = Gd, Tm, and Lu, INA = isonicotinic acid, GA = glycolic acid) single crystals, where electrons are found to transport along the π-π stacked aromatic carbon rings in the crystals. The show remarkable stability, with minimal changes in conductivity under varying solution pH (1-12), temperature (373 K), and electric field as high as 800 000 V/m. This stability is achieved through the formation of strong coordination bonds between high-valent Ln(III) ions and rigid carboxylic linkers as well as hydrogen bonds that enhance the robustness of the electron transport path. The demonstrated lanthanide MOFs pave the way for the design of stable and conductive MOFs.
导电金属有机框架材料(MOFs)因其在能源相关技术和传感器中的潜在应用而受到广泛研究。然而,要实现这一目标,需要MOFs具有高度稳定性,并在不同溶液环境和温度的实际操作条件下保持其导电性。在此,我们设计并合成了一系列新的{Ln(μ-O)(μ-OH)(INA)(GA)(HO)}(表示为 ,Ln = Gd、Tm和Lu,INA = 异烟酸,GA = 乙醇酸)单晶,其中发现电子沿着晶体中的π-π堆积芳香碳环传输。这些单晶表现出显著的稳定性,在不同溶液pH值(1 - 12)、温度(373 K)以及高达800 000 V/m的电场下,电导率变化极小。这种稳定性是通过高价Ln(III)离子与刚性羧酸连接体之间形成强配位键以及增强电子传输路径稳健性的氢键来实现的。所展示的镧系MOFs为稳定且导电的MOFs设计铺平了道路。