Coordination Assembly of the Water‐Soluble Ti₄(embonate)₆ Cages with Mn²⁺ Ions

Abstract

In the past decades, great efforts have been devoted to the design and self‐assembly of discrete metal‐organic cages (MOCs). The further assembly of cages into advanced supramolecular materials is relatively less developed. Previously, we reported a water‐soluble Ti4L6 cage (L=embonate), which has been applied as the starting material to realize coordination assembly with different metal ions through two‐step reaction. In this work, by employing the Ti4L6 cages to assemble with Mn2+ ions in the presence of piperazine and melamine, a Ti4L6−Mn2 cage and a Z‐shaped Ti4L6−Mn2 chain structure have been synthesized and structurally characterized, respectively.

Syntheses and Structural Studies of a Series of Ti4(embonate)6-based Complexes

“…2017 年, 在前人的研究基础上, 本课题组 [35] 通过选 用含有多个氧配位点的帕莫酸(L)作为配体, 构筑了首 例可溶于水、超稳定且具有配位组装功能的 Ti 4 L 6 四面 体笼(PTC-101, (Me 2 NH 2 ) 8 (Ti 4 L 6 )•Guests). 值得指出的 是, 以 PTC-101 为起始材料, 通过二步法, 实现了其与 不同金属离子以及混合含氮类辅助有机配体的配位组 装 [36][37][38] .另外, 由原位生成的单手性的[Mn(1,2-DCH) 3 ]-(1,2-DCH＝1,2-环己二胺)单元通过氢键作用, 我们成功 对两种构型(Δ,Δ,Δ,Δ 和 Λ,Λ,Λ,Λ)的 Ti 4 L 6 笼进行了拆分, 图式 1 基于 Ti 4 L 6 笼的多步自组装 Scheme 1 Illustration of the stepwise self-assembly based on Ti 4 L 6 cage 并将其应用于手性分子(扁桃酸和萘普生)的识别 [39] . ＋ and en, respectively; (c) 3D packing supramolecular framework.…”