Chen Yun, Li Changyun, Wang Xuefei, Fan Li, Zhang Yongxia, Zhao Xinsheng, Li Qiu-Yan, Wang Xiao-Jun
Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou 221116, P. R. China.
Inorg Chem. 2024 Oct 21;63(42):19924-19930. doi: 10.1021/acs.inorgchem.4c03387. Epub 2024 Oct 10.
As a prototypical aggregation-induced emission luminogen (AIEgen), the tetraphenylethene (TPE) moiety has been judiciously modified as organic linkers for constructing various functional metal-organic frameworks (MOFs). However, these AIEgen-based MOFs have rarely received research attention in photocatalytic applications due to their limited stability in harsh reaction conditions. In this work, we report a robust Ni-pyrazolate-based MOF (denoted as TPE4Pz-Ni) under the guidance of reticular chemistry, which is assembled by an AIE-active tetratopic linker of 1,1,2,2-tetrakis(4-(1-pyrazol-4-yl)phenyl)ethane (H-TPE4Pz) with a 12-connected Ni-cluster of [Ni(OH)(HO)Pz] (Pz = pyrazolate) in a (4,12)-connected -a topological network. Notably, MOF TPE4Pz-Ni exhibits excellent stability in a wide range of solvents and even in a saturated NaOH solution. Moreover, its luminescent emission is effectively quenched via a ligand-to-metal charge transfer (LMCT) process originating from the TPE-cored linker to the Ni cluster, which enables TPE4Pz-Ni to act as an efficient photoredox/nickel dual catalyst for light-mediated C-S cross-coupling reactions between various aryl iodides and thiols.
作为一种典型的聚集诱导发光材料（AIEgen），四苯乙烯（TPE）部分已被巧妙地修饰为有机连接体，用于构建各种功能金属有机框架（MOF）。然而，由于这些基于AIEgen的MOF在苛刻反应条件下稳定性有限，它们在光催化应用中很少受到研究关注。在这项工作中，我们在网状化学的指导下报道了一种稳健的基于吡唑镍的MOF（记为TPE4Pz-Ni），它由1,1,2,2-四（4-（1-吡唑-4-基）苯基）乙烷（H-TPE4Pz）的AIE活性四齿连接体与[Ni(OH)(HO)Pz]（Pz = 吡唑酸盐）的12连接镍簇在（4,12）连接的-a拓扑网络中组装而成。值得注意的是，MOF TPE4Pz-Ni在广泛的溶剂中甚至在饱和NaOH溶液中都表现出优异的稳定性。此外，其发光发射通过源自TPE核心连接体到镍簇的配体到金属电荷转移（LMCT）过程有效地猝灭，这使得TPE4Pz-Ni能够作为一种高效的光氧化还原/镍双催化剂，用于各种芳基碘化物和硫醇之间的光介导C-S交叉偶联反应。
