Wang Lei, Sarkar Arup, Grocke Garrett L, Laorenza Daniel William, Cheng Baorui, Ritchhart Andrew, Filatov Alexander S, Patel Shrayesh N, Gagliardi Laura, Anderson John S
Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United States.
J Am Chem Soc. 2023 Apr 5. doi: 10.1021/jacs.3c00495.
Two-dimensional (2D) inorganic materials have emerged as exciting platforms for (opto)electronic, thermoelectric, magnetic, and energy storage applications. However, electronic redox tuning of these materials can be difficult. Instead, 2D metal-organic frameworks (MOFs) offer the possibility of electronic tuning through stoichiometric redox changes, with several examples featuring one to two redox events per formula unit. Here, we demonstrate that this principle can be extended over a far greater span with the isolation of four discrete redox states in the 2D MOFs ( = 0-3, THT = triphenylenehexathiol). This redox modulation results in 10,000-fold greater conductivity, p- to n-type carrier switching, and modulation of antiferromagnetic coupling. Physical characterization suggests that changes in carrier density drive these trends with relatively constant charge transport activation energies and mobilities. This series illustrates that 2D MOFs are uniquely redox flexible, making them an ideal materials platform for tunable and switchable applications.
二维（2D）无机材料已成为用于（光）电子、热电、磁性和能量存储应用的令人兴奋的平台。然而，对这些材料进行电子氧化还原调节可能很困难。相反，二维金属有机框架（MOF）提供了通过化学计量的氧化还原变化进行电子调节的可能性，有几个例子表明每个化学式单元有一到两个氧化还原事件。在这里，我们证明，通过在二维MOF（= 0 - 3，THT = 三亚苯六硫醇）中分离出四种离散的氧化还原状态，这一原理可以扩展到更大的范围。这种氧化还原调制导致电导率提高10000倍，实现了p型到n型载流子的切换，并调制了反铁磁耦合。物理表征表明，载流子密度的变化推动了这些趋势，同时电荷传输活化能和迁移率相对恒定。该系列表明二维MOF具有独特的氧化还原灵活性，使其成为用于可调谐和可切换应用的理想材料平台。
