Linear Components for Supramolecular Networks超分子网络的线性组件.pdfVIP

1 Linear Components for Supramolecular Networks 1.1 Flexible Components The origins of supramolecular chemistry are intimately linked to Pedersen’s pio- neering work on crown ethers. His fortuitous discovery of dibenzo[18]crown-6 in 1967 occurred when he was attempting to prepare a flexible phenol-terminated polyether which was expected to bind to the vanadyl ion and thus support its catalytic activity [1]. Although the importance of the new class of cyclic polyethers was recognized across the globe, researchers were also alerted to Pedersen’s original goal: the potential for acyclic polyethers to act as metal- binding ligands. Starting points for many of the experiments were the widely available polyethylene glycols that could be modified readily. Foremost among ¨ those preparing functionalized polyethers were Vogtle and Weber who coined the term ‘podands’ for their compounds [2]. Polyethers are well known for their abilities to wrap around metal ions, particularly those in groups 1 and 2 and the lanthanides (Figure 1.1), but the intro- duction of coordinating termini in concert with variable lengths of the polyether tether gave greater specificity to the ligands [3,4]. More recently, polyethers have been used to prepare coordination networks through the incorporation of transition metals. The inherent flexibility of the ether link coupled to the preferred geometry of certain metals gives rise to some very interesting nanoscale complexes, many of which have a helical motif [5]. Two methods to prepare polyether-based podands are described here. The first is a direct modification of polyethylene glycols and comes originally from the work of Piepers and Kellogg [6], later modified by Hosseini [7]. A simple reaction between hexaethylene glycol and isonicotiny