Wang Lei, Papoular Robert J, Horwitz Noah E, Xie Jiaze, Sarkar Arup, Campisi Dario, Zhao Norman, Cheng Baorui, Grocke Garrett L, Ma Tengzhou, Filatov Alexander S, Gagliardi Laura, Anderson John S
Department of Chemistry, University of Chicago, 5735 S Ellis Ave, Chicago, IL 60637, USA.
IRAMIS, Leon Brillouin Laboratory, CEA-Saclay, 91191, Gif-sur-Yvette, France.
Angew Chem Int Ed Engl. 2022 Nov 7;61(45):e202207834. doi: 10.1002/anie.202207834. Epub 2022 Oct 7.
The emergence of conductive 2D and less commonly 3D coordination polymers (CPs) and metal-organic frameworks (MOFs) promises novel applications in many fields. However, the synthetic parameters for these electronically complex materials are not thoroughly understood. Here we report a new 3D semiconducting CP Fe (C O ) , which is a fusion of 2D Fe-semiquinoid materials and 3D cubic Fe (C O ) materials, by using a different initial redox-state of the C O linker. The material displays high electrical conductivity (0.02 S cm ), broad electronic transitions, promising thermoelectric behavior (S σ=7.0×10 W m K ), and strong antiferromagnetic interactions at room temperature. This material illustrates how controlling the oxidation states of redox-active components in conducting CPs/MOFs can be a "pre-synthetic" strategy to carefully tune material topologies and properties in contrast to more commonly encountered post-synthetic modifications.
导电二维（较少见的三维）配位聚合物（CPs）和金属有机框架（MOFs）的出现为许多领域带来了新的应用前景。然而，这些电子结构复杂的材料的合成参数尚未得到充分理解。在此，我们报道了一种新型三维半导体CP Fe(CO)，它是通过使用CO连接体的不同初始氧化还原态，将二维铁半醌材料和三维立方Fe(CO)材料融合而成。该材料具有高电导率（0.02 S cm）、宽电子跃迁、良好的热电性能（Sσ = 7.0×10 W m K），并且在室温下具有强反铁磁相互作用。这种材料表明，与更常见的合成后修饰相比，控制导电CPs/MOFs中氧化还原活性成分的氧化态可以作为一种“合成前”策略，用于精细调节材料的拓扑结构和性能。
