通过多光谱技术研究了TCNQ负载的Cu3（BTC）2中的孔化学和Cu（I）缺陷的重要性。,ACS Applied Materials & Interfaces

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通过多光谱技术研究了TCNQ负载的Cu3（BTC）2中的孔化学和Cu（I）缺陷的重要性。
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2019-12-24 , DOI: 10.1021/acsami.9b16663
Christian Schneider ₁ , Matthias Mendt ₂ , Andreas Pöppl ₂ , Valentina Crocellà ₃ , Roland A Fischer ₁

Affiliation

主客体相互作用控制了多孔材料在许多应用中的基本过程，例如气体存储和催化。然而，即使材料是晶体，对这些过程的研究也不是简单的。特别是金属有机骨架（MOF）代表了一种复杂的情况，因为客体分子可以与有机连接基和金属簇的不同部分相互作用，并可能改变孔结构和系统特性的细节。一个突出的例子是所谓的MOF改良材料TCNQ @ Cu3（BTC）2，由于其由宿主-客体相互作用引起的电子特性而引起了广泛的关注。直到最近，有关TCNQ与两个Cu桨轮单元的桥接结合模式的结构证据才被提出。然而，目前尚未解决有关Cu3（BTC）2和TCNQ的氧化还原化学的许多问题。在这里，我们报告了一种强大的光谱方法来研究这种材料的客体-客体化学。结合在CO和EPR光谱存在下的IR光谱，我们发现主体的固有Cu（I）缺陷与客体反应，形成TCNQ自由基阴离子。这种化学性质具有深远的意义，特别是在TCNQ @ Cu3（BTC）2作为电子导体的性能方面。随着TCNQ负荷的增加，开放的Cu（II）位点的可用性降低，证明了TCNQ与桨轮结点的配位结合，并且在低TCNQ负荷下形成了具有不同TCNQ排列和孔隙环境的异质结构。最后，结合使用光谱表征技术已被证明是，

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Scrutinizing the Pore Chemistry and the Importance of Cu(I) Defects in TCNQ-Loaded Cu3(BTC)2 by a Multitechnique Spectroscopic Approach.

Host-guest interactions control the fundamental processes in porous materials for many applications such as gas storage and catalysis. The study of these processes, however, is not trivial, even if the material is crystalline. In particular, metal-organic frameworks (MOFs) represent a complex situation since guest molecules can interact with different parts of the organic linkers and the metal clusters and may alter the details of the pore structure and system properties. A prominent example is the so-called retrofitted MOF material TCNQ@Cu3(BTC)2 that has attracted a lot of attention due to its electronic properties induced by the host-guest interactions. Only recently, structural evidence has been presented for a bridging binding mode of TCNQ to two Cu paddlewheel units; however, many issues regarding the redox chemistry of Cu3(BTC)2 and TCNQ are currently unsolved. Herein, we report a powerful spectroscopic approach to study the host-guest chemistry of this material. Combining IR spectroscopy in the presence of CO and EPR spectroscopy, we found that the intrinsic Cu(I) defects of the host react with the guest, forming TCNQ radical anions. This chemistry has profound implications, in particular, with respect to the performance of TCNQ@Cu3(BTC)2 as an electronic conductor. A decreasing availability of open Cu(II) sites with increasing TCNQ loading proves the coordinative binding of TCNQ to the paddlewheel nodes, and a heterogeneous structure is formed with different TCNQ arrangements and pore environments at low TCNQ loadings. Finally, the combined use of spectroscopic characterization techniques has proven to be, in general, a powerful approach for studying the complex chemistry of host-guest materials.

更新日期：2019-12-25

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