Graduate School of Pure and Applied Sciences and Tsukuba Research Center for Interdisciplinary Materials Science (TIMS), University of Tsukuba , 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan.
J Am Chem Soc. 2016 Jan 27;138(3):794-7. doi: 10.1021/jacs.5b12752. Epub 2016 Jan 14.
The hierarchical organization strategy has realized elaborate supramolecular structures that are difficult to achieve by a one-pot thermodynamically driven self-assembly. Self-assembly via Schiff base formation of the preorganized tripodal helical unit 2(2+), which is composed of the tris(bipyridyl) ligand 1 and octahedral metal ion (Ru(II) and Fe(II)), lead to two supramolecular structures, i.e., a macrobicyclic dimer and an interlocked helicate. Notably, the interlocked helicate had a unique motif with an elongated shape (∼ 58 Å) and linearly aligned metal centers with homochiral configurations (all-Δ or all-Λ), which shows potential for allosteric regulation based on the long-range transmittance of the structural information.
层级组织策略实现了精细的超分子结构,这是通过一锅热驱动力自组装难以实现的。通过预组织的三脚螺旋单元 2(2+)的席夫碱形成进行自组装,该单元由三(联吡啶)配体 1 和八面体金属离子(Ru(II)和 Fe(II))组成,导致了两种超分子结构,即大环二聚体和互锁螺旋体。值得注意的是,互锁螺旋体具有独特的拉长形状(约 58 Å)和线性排列的手性金属中心(全Δ或全Λ),这表明基于结构信息的远程传递具有变构调节的潜力。