Kim Seulgi, An Jaewook, Choi Heekyoung, Jung Sung Ho, Lee Shim Sung, Park In-Hyeok
Department of Chemistry and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 52828, South Korea.
Graduate School of Analytical Science and Technology (GRAST), Chungnam National University, Daejeon 34134, South Korea.
Inorg Chem. 2023 Aug 21;62(33):13173-13178. doi: 10.1021/acs.inorgchem.3c02349. Epub 2023 Aug 8.
Chiral metal-organic frameworks (CMOFs) and solid-state [2 + 2] photocyclization have been explored as independent areas in crystal engineering. We herein report the photoreactive CMOFs that undergo a [2 + 2] photocycloaddition reaction for the first time. Through the incorporation of a dipyridyl olefin ligand, 1,4-bis[2-(4-pyridyl)ethenyl]benzene, and d-camphoric acid or l-camphoric acid, we constructed a pair of homochiral Zn(II) CMOFs (d- or l-) with a two-dimensional sql topology via a two-step procedure to avoid racemization. Both d- and l- were photoinert due to the large olefin bond separation. The removal of the solvent molecules between layers enabled them (d- and l-) to undergo [2 + 2] cycloaddition reactions; d- is more reactive (70%) than l- (20%) probably due to proper desolvation-induced rearrangement. The photoluminescence properties are also discussed. This work presents a new perspective on photoreactive homochiral network materials with diverse topologies and applications.
手性金属有机框架（CMOFs）和固态[2 + 2]光环化反应已作为晶体工程中的独立领域进行了探索。我们在此首次报道了能发生[2 + 2]光环加成反应的光反应性CMOFs。通过引入二吡啶基烯烃配体1,4 - 双[2 -（4 - 吡啶基）乙烯基]苯以及d - 樟脑酸或l - 樟脑酸，我们通过两步法构建了一对具有二维sql拓扑结构的手性Zn（II）CMOFs（d - 或l -），以避免消旋化。由于烯烃键间距较大，d - 和l - 两者均为光惰性的。去除层间溶剂分子使它们（d - 和l -）能够发生[2 + 2]环加成反应；d - 的反应活性（70%）比l -（20%）更高，这可能是由于适当的去溶剂化诱导重排所致。还讨论了其光致发光性质。这项工作为具有多样拓扑结构和应用的光反应性手性网络材料提供了新的视角。
