Zeni Willi, Müller Danny, Artner Werner, Giester Gerald, Reissner Michael, Weinberger Peter
Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163-01-3, 1060 Vienna, Austria.
X-Ray Center, TU Wien, Getreidemarkt 9/057-4, 1060 Vienna, Austria.
Inorg Chem. 2024 Sep 16;63(37):17067-17076. doi: 10.1021/acs.inorgchem.4c02732. Epub 2024 Sep 3.
The combination of spin crossover (SCO) with guest incorporation properties has attracted the interest of researchers in the last couple of decades and has led to the design of numerous SCO porous coordination polymers (SCO-PCPs). The most famous class of SCO-PCPs is the Hofmann-type network, which is a very promising material for (chemo)sensing applications. Different strategies have been carried out to expand the classic structure {Fe(pz)[M(CN)]} (M = Ni, Pd, Pt) to get larger cavities, but the resulting compounds often showed a poor magnetic behavior. In this work, we present wide-mesh-size spin-switching Hofmann-type networks based on tetrakis-cyanoacetylides synthesized with a newly developed method, resulting in compounds with the general formula {Fe(pz)[M(CN)]} (M=Ni, Pd, Pt). The compounds were characterized in their structural, magnetic, and spectroscopic properties. They present 5-fold larger cavities and a drastic increase in porosity. The desired hysteretic and guest-dependent spin-crossover behavior is retained, and in situ chemo-switching of the spin state and the memory effect are also observed.
在过去几十年里，自旋交叉（SCO）与客体容纳特性的结合吸引了研究人员的关注，并促使人们设计出众多的SCO多孔配位聚合物（SCO-PCP）。最著名的一类SCO-PCP是霍夫曼型网络，它是一种非常有前途的用于（化学）传感应用的材料。人们已经采用了不同的策略来扩展经典结构{Fe(pz)[M(CN)]}（M = Ni、Pd、Pt）以获得更大的空腔，但所得化合物的磁行为往往较差。在这项工作中，我们展示了基于用新开发方法合成的四氰基乙炔化物的宽网孔尺寸自旋切换霍夫曼型网络，得到了通式为{Fe(pz)[M(CN)]}（M = Ni、Pd、Pt）的化合物。对这些化合物的结构、磁性和光谱性质进行了表征。它们具有大5倍的空腔且孔隙率急剧增加。保留了所需的滞后和客体依赖性自旋交叉行为，并且还观察到了自旋态的原位化学切换和记忆效应。
