ABSTRACT
The tetradehydro-Diels-Alder (TDDA) reaction is a useful transformation for the rapid assembly of polycyclic scaffolds from simple linear precursors in a single synthetic step. However, the reaction requires careful substrate design and harsh reaction conditions to overcome the inherent entropic cost for this transformation. Herein we report an efficient site-selective TDDA transformation within a self-assembled Pd6L4 cage. Despite the large size, the flexibility of the employed substrates allows for efficient encapsulation within the host cavity. The rate of thermal cyclization of the encapsulated guest was found to be greatly enhanced, and high product selectivity for an unsymmetrical substrate was observed. The efficiency of this system relies on the precise conformational control of the substrate within the confined space of the host cage.
ABSTRACT
Free-standing, ultralong (up to several millimeters) nanobelts of gold, silver, and copper were fabricated by a template approach. Firstly, a metal nanofin array was prepared on a substrate via metal nanocoating of the template surface and selective removal of the metal top layer and template. Electroless plating and sputtering were employed for the metal nanocoating. In this approach, the minimum width and thickness of the Au nanobelt were 95 and 30 nm, respectively. Systematic control of the nanobelt width (from 95 to 350 nm) was successfully achieved by adjusting the template height. Free-standing nanobelts of several millimeters in length were fabricated and maintained their unique structure and alignment, even on a mesh grid.
