Grabicki Niklas, Fisher Sergey, Dumele Oliver
Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489, Berlin, Germany.
Angew Chem Int Ed Engl. 2023 Apr 11;62(16):e202217917. doi: 10.1002/anie.202217917. Epub 2023 Mar 9.
An ethylene glycol-decorated [6]cyclo-meta-phenylene (CMP) macrocycle was synthesized and utilized as a subunit to construct a fourfold Au -aryl metallacycle with an overall square arrangement. The corners consist of rigid dinuclear gold(I) complexes previously known to form only triangular metallacycles. The interplay between the conformational flexibility of the [6]CMP macrocycle and the rigid dinuclear gold(I) moieties enable the square geometry, as revealed by single-crystal X-ray diffraction. The formation of the gold complex shows size-selectivity compared to an alternative route using platinum(II) corner motifs. Upon reductive elimination, an all-organic ether-decorated carbon nanoring was obtained. Investigation as a host for the complexation of large guest molecules with a suitable convex π-surfaces was accomplished using isothermal NMR binding titrations. Association constants for [6]cycloparaphenylene ([6]CPP), [7]CPP, C , and C were determined.
合成了一种乙二醇修饰的[6]环间亚苯基（CMP）大环，并将其用作构建具有整体方形排列的四重金-芳基金属环的亚基。角部由先前已知仅形成三角形金属环的刚性双核金（I）配合物组成。如单晶X射线衍射所示，[6]CMP大环的构象灵活性与刚性双核金（I）部分之间的相互作用使得形成方形几何结构。与使用铂（II）角基序的另一种路线相比，金配合物的形成表现出尺寸选择性。经还原消除后，得到了一种全有机醚修饰的碳纳米环。使用等温NMR结合滴定法研究了其作为具有合适凸π表面的大型客体分子络合主体的情况。测定了[6]环对亚苯基（[6]CPP）、[7]CPP、C和C的缔合常数。
