Zhao Yan-Wu, Guo Li-E, Zhang Fu-Qiang, Yao Jin, Zhang Xian-Ming
Key Laboratory of Magnetic Molecules & Magnetic Information Materials, Ministry of Education, School of Chemistry & Material Science, Shanxi Normal University, Linfen, Shanxi 041004, P. R. China.
College of Chemistry & Chemical Engineering, Key Laboratory of Interface Science and Engineering in Advanced Material, Ministry of Education,Taiyuan University of Technology, No. 79 Yingze West, Taiyuan, Shanxi 030024, P. R. China.
ACS Appl Mater Interfaces. 2021 May 5;13(17):20821-20829. doi: 10.1021/acsami.1c02897. Epub 2021 Apr 22.
Two-dimensional (2D) metal-organic frameworks (MOFs) have attracted growing interest due to excellent performance in gas separation, energy conversion and storage, catalysis, and sensing, but their homochirality and exfoliation as well as related enantioselective catalysis and sensing remain a stage of pending exploration owing to the scarcity of homochiral MOFs and intrinsic aggregation of nanosheets. Herein, a homochiral 2D MOF (HMOF-3) with polymeric chirality, good thermostability, and solvent stability is designed and constructed by a homochiral organic ligand 5,5'-((1,2)-cyclohexane dicarbonyl bis(azanediyl)) diisophthalic acid (,-CHCAIP), a ditopic coligand 4,4'-bipyridine, and Zn salts. Remarkably, HMOF-3 can be exfoliated via solvent-assisted sonication to achieve 2D HMOF-3 nanosheets (HMOF-3-NS), which exhibit a sensitive turn-on effect with the fluorescence enhancement up to 63.5 times in the presence of /-mandelic acid, d/l-tartaric acid, d/l-lactic acid, d/l-alanine, and d/l-tryptophan. More importantly, the high surface area, polymeric chirality environment, and highly accessible functional sites on the surface of HMOF-3 nanosheets enable close contact with probed enantiomers, leading to highly enantioselective and sensitive sensing. The turn-on mechanism of host-guest-assisted electronic transfer is confirmed by DFT calculation and the relative experiment. This work highlights the promise of homochiral 2D MOF nanosheets for enantioselective sensing applications.
二维(2D)金属有机框架(MOF)因其在气体分离、能量转换与存储、催化及传感等方面的优异性能而受到越来越多的关注。然而,由于手性纯MOF的稀缺以及纳米片的固有聚集,它们的同手性、剥离以及相关的对映选择性催化和传感仍处于有待探索的阶段。在此,通过手性纯有机配体5,5'-((1,2)-环己烷二羰基双(氮杂二亚基))二间苯二甲酸(,-CHCAIP)、双齿共配体4,4'-联吡啶和锌盐设计并构建了一种具有聚合物手性、良好热稳定性和溶剂稳定性的手性纯2D MOF(HMOF-3)。值得注意的是,HMOF-3可通过溶剂辅助超声处理进行剥离,以获得2D HMOF-3纳米片(HMOF-3-NS),其在存在/-扁桃酸、d/l-酒石酸、d/l-乳酸、d/l-丙氨酸和d/l-色氨酸时表现出灵敏的开启效应,荧光增强高达63.5倍。更重要的是,HMOF-3纳米片的高比表面积、聚合物手性环境以及表面高度可及的功能位点能够与被探测的对映体紧密接触,从而实现高度对映选择性和灵敏的传感。通过密度泛函理论计算和相关实验证实了主客体辅助电子转移的开启机制。这项工作突出了手性纯2D MOF纳米片在对映选择性传感应用中的前景。