Chatterjee Biswaroop, Noveron Juan C, Resendiz Marino J E, Liu Jie, Yamamoto Takuya, Parker Daniel, Cinke Martin, Nguyen Cattien V, Arif Atta M, Stang Peter J
Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, USA.
J Am Chem Soc. 2004 Sep 1;126(34):10645-56. doi: 10.1021/ja0388919.
The syntheses, structures, and N2 adsorption properties of six new supramolecular metallacycles are reported. Flexible ditopic linkers, 1-4, with systematically varied lengths and conformational degrees of freedom were synthesized utilizing ester linkages. They were used in combination with (dppp)M(OTf)2, where M = Pt(II) and Pd(II), and cis-(Me3P)2Pt(OTf)2 to form flexible supramolecular metallacycles 5-10 in 88-98% isolated yields. Their structures were characterized via multinuclear NMR and X-ray crystallography. The metallacycles stack to form porous structures in the crystalline state. The pore dimensions depend on both the phosphorus ligands attached to the metals and the flexible linkers. Adsorption studies on the porous materials show that 5a, 6, 8, and 9 held 11.7, 16.5, 5.7, and 6.8 cm3/g STP of N2 at 77 K, respectively. A guest-exchange study with nitromethane and toluene reveals that the nanopore in 5 is flexible, a property which was transferred from the linker to the supramolecular structure in the solid state.
报道了六种新型超分子金属环的合成、结构及N₂吸附性能。利用酯键合成了具有系统变化长度和构象自由度的柔性双齿连接体1 - 4。它们与(dppp)M(OTf)₂（其中M = Pt(II)和Pd(II)）以及顺式-(Me₃P)₂Pt(OTf)₂组合使用，以88 - 98%的分离产率形成柔性超分子金属环5 - 10。通过多核NMR和X射线晶体学对其结构进行了表征。金属环在晶体状态下堆积形成多孔结构。孔尺寸取决于连接到金属上的磷配体和柔性连接体。对多孔材料的吸附研究表明，在77 K时，5a、6、8和9分别吸附11.7、16.5、5.7和6.8 cm³/g STP的N₂。用硝基甲烷和甲苯进行的客体交换研究表明，5中的纳米孔是柔性的，这种性质从连接体转移到了固态的超分子结构中。
