Röß-Ohlenroth Richard, Kraft Maryana, Bunzen Hana, Volkmer Dirk
Chair of Solid State and Materials Chemistry, Institute of Physics, University of Augsburg, Universitätsstr. 1, D-86159 Augsburg, Germany.
Inorg Chem. 2022 Oct 17;61(41):16380-16389. doi: 10.1021/acs.inorgchem.2c02394. Epub 2022 Oct 5.
Triazolate-based MFU-4-type metal-organic frameworks are promising candidates for various applications, of which heterogeneous catalysis has emerged as a hot topic owing to the facile post-synthetic metal and ligand exchange in Kuratowski secondary building units (SBUs). Herein, we present the largest non-interpenetrated isoreticular MFU-4-type framework ([CoCl(H-bibt)]; H-bibt = 1,1',5,5'-tetrahydro-6,6'-biimidazo[4,5-]benzotriazole; CFA-19 = Coordination Framework Augsburg University-19) and the derivative featuring trispyrazolylborate inhibited SBUs as a scaffold with open bibenzimidazole coordination sites at the backbone of the linker. The proof-of-principle incorporation of accessible MBr(CO) (M = Re, Mn) sites in was revealed by single-crystal X-ray diffraction, and a thermally induced CO release was observed for MnBr(CO). Deprotonation of bibenzimidazole was also achieved by the reaction with ZnEt.
基于三唑的MFU-4型金属有机框架是各种应用的有前途的候选材料，其中多相催化由于在库拉托夫斯基二级构筑单元（SBUs）中易于进行合成后金属和配体交换而成为一个热门话题。在此，我们展示了最大的非互穿等规MFU-4型框架（[CoCl(H-bibt)]；H-bibt = 1,1',5,5'-四氢-6,6'-联咪唑并[4,5-]苯并三唑；CFA-19 = 奥格斯堡大学配位框架-19）以及一种衍生物，该衍生物以三吡唑基硼酸酯抑制的SBUs为支架，在连接体的主链上具有开放的联苯并咪唑配位位点。通过单晶X射线衍射揭示了在其中可接近的MBr(CO)（M = Re、Mn）位点的原理验证掺入，并且观察到MnBr(CO)有热诱导的CO释放。通过与ZnEt反应也实现了联苯并咪唑的去质子化。
