Turunen Lotta, Peuronen Anssi, Forsblom Samu, Kalenius Elina, Lahtinen Manu, Rissanen Kari
University of Jyvaskyla, Department of Chemistry, NanoScience Center, P.O. Box 35, 40014, Jyvaskyla, Finland.
Chemistry. 2017 Aug 25;23(48):11714-11718. doi: 10.1002/chem.201702655. Epub 2017 Jul 27.
Tripodal N-donor ligands are used to form halogen-bonded assemblies via structurally analogous Ag -complexes. Selective formation of discrete tetrameric I L and dimeric I L halonium cages, wherein multiple [N⋅⋅⋅I ⋅⋅⋅N] halogen bonds are used in concert, can be achieved by using sterically rigidified cationic tris(1-methyl-1-azonia-4-azabicyclo[2.2.2]octane)-mesitylene ligand, L1(PF ) , and flexible ligand 1,3,5-tris(imidazole-1-ylmethyl)-2,4,6-trimethylbenzene, L2, respectively. The iodonium cages, I L1 (PF ) and I L2 (PF ) , were obtained through the [N⋅⋅⋅Ag ⋅⋅⋅N]→ [N⋅⋅⋅I ⋅⋅⋅N] cation exchange reaction between the corresponding Ag L1 (PF ) and Ag L2 (PF ) coordination cages, prepared as intermediates, and I . The synthesized metallo- and halonium cages were studied in solution by NMR, in gas phase by ESI-MS and in the solid-state by single crystal X-ray diffraction.
三脚架型氮供体配体用于通过结构类似的银配合物形成卤素键合组装体。通过使用空间刚性的阳离子三（1-甲基-1-氮杂-4-氮杂双环[2.2.2]辛烷）-均三甲苯配体L1(PF)和柔性配体1,3,5-三（咪唑-1-基甲基）-2,4,6-三甲基苯L2，分别可以实现离散四聚体IL和二聚体IL卤鎓笼的选择性形成，其中多个[N⋅⋅⋅I ⋅⋅⋅N]卤素键协同作用。卤鎓笼IL1(PF)和IL2(PF)是通过作为中间体制备的相应AgL1(PF)和AgL2(PF)配位笼与I之间的[N⋅⋅⋅Ag ⋅⋅⋅N]→[N⋅⋅⋅I ⋅⋅⋅N]阳离子交换反应获得的。通过核磁共振在溶液中、通过电喷雾电离质谱在气相中以及通过单晶X射线衍射在固态中对合成的金属笼和卤鎓笼进行了研究。
