Wang Chen, Zeng Guang, You Zi-Xin, Xing Yong-Heng, Bai Feng-Ying, Sun Li-Xian
College of Chemistry and Chemical Engineering, Liaoning Normal University, Huanghe Road 850#, Dalian 116029, P. R. China.
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian 116023, P. R. China.
Inorg Chem. 2022 Jul 4;61(26):10066-10078. doi: 10.1021/acs.inorgchem.2c01007. Epub 2022 Jun 21.
A series of novel Cd metal-organic frameworks (MOFs) (-) with different extended spacers with seven kinds of the aliphatic dicarboxylic acids as secondary building linkers based on ,'-di(4-pyridylacylamino)-1,4,5,8-naphthalenediimide (NDI-A) have been designed and synthesized by changing the volume ratio of solvents under solvothermal conditions. In addition, the secondary building linkers of aliphatic dicarboxylic acids have different spacer lengths, resulting in different structures of complexes -. So, their packing structures are affected by the degree of distortion of the NDI-A ligand, the different aliphatic dicarboxylic acids ligands, and the hydrogen-bonding patterns. Complexes - showed stimuli-responsive emission tuned by different aliphatic dicarboxylic acids with extended length spacers under UV light irradiation, accompanied by the color change from light orange to dark brown, and achieved reversible photochromic under heating, which indicates that they could serve as secret erasable inks. Moreover, complexes - exhibited selective vaporchromic behavior to methylamine (MA), and the vaporchromic sample could be recovered after washing with MeOH. It is worth noting that the preparation of poly(vinyl alcohol) (PVA)-NDI-MOF films enables the photochromic and vaporchromic properties of complexes - to apply in practice. In addition, complexes - exhibited good fluorescence properties as sensing probes toward 2,4,6-trinitrophenol (TNP) with lower limits of detection. In short, this work provides a broad field to explore the creative NDI-MOF materials with photoactive and luminescent properties.
基于1,4'-二(4-吡啶甲酰胺基)-1,4,5,8-萘二酰亚胺(NDI-A)，通过在溶剂热条件下改变溶剂的体积比，设计并合成了一系列具有不同扩展间隔基的新型镉金属有机框架(MOF)(-)，其中七种脂肪族二羧酸作为二级构建连接体。此外，脂肪族二羧酸的二级构建连接体具有不同的间隔基长度，导致配合物(-)的结构不同。因此，它们的堆积结构受到NDI-A配体的扭曲程度、不同的脂肪族二羧酸配体以及氢键模式的影响。配合物(-)在紫外光照射下表现出由不同脂肪族二羧酸调节的刺激响应发射，间隔基长度延长，伴随着颜色从浅橙色变为深棕色，并在加热下实现可逆光致变色，这表明它们可以用作秘密可擦除墨水。此外，配合物(-)对甲胺(MA)表现出选择性气致变色行为，气致变色样品用甲醇洗涤后可以恢复。值得注意的是，聚(乙烯醇)(PVA)-NDI-MOF薄膜的制备使配合物(-)的光致变色和气致变色性能能够实际应用。此外，配合物(-)作为对2,4,6-三硝基苯酚(TNP)的传感探针表现出良好的荧光性能，检测下限较低。简而言之，这项工作为探索具有光活性和发光性能的新型NDI-MOF材料提供了广阔的领域。
