Zhang Fangyuan, Radacki Krzysztof, Braunschweig Holger, Lambert Christoph, Ravat Prince
Institut für Organische Chemie, Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Angew Chem Int Ed Engl. 2021 Oct 25;60(44):23656-23660. doi: 10.1002/anie.202109380. Epub 2021 Sep 28.
In this communication, we demonstrate a novel approach to prepare a discrete dimer of chiral phthalocyanine (Pc) by exploiting the flexible molecular geometry of helicenes, which enables structural interlocking and strong aggregation tendency of Pcs. Synthesized [7]helicene-Pc hybrid molecular structure, zinc-[7]helicenocyanine (Zn-7HPc), exclusively forms a stable dimeric pair consisting of two homochiral molecules. The dimerization constants were estimated to be as high as 8.96×10 M and 3.42×10 M in THF and DMSO, respectively, indicating remarkable stability of dimer. In addition, Zn-7HPc exhibited chiral self-sorting behavior, which resulted in preferential formation of a homochiral dimer also in the racemic sample. Two phthalocyanine subunits in the dimeric form strongly communicate with each other as revealed by a large comproportionation constant and observation of an IV-CT band for the thermodynamically stable mixed-valence state.
在本通讯中，我们展示了一种通过利用螺旋烯的柔性分子几何结构来制备手性酞菁（Pc）离散二聚体的新方法，该结构能够实现酞菁的结构互锁和强烈聚集趋势。合成的[7]螺旋烯 - Pc杂化分子结构，即锌 - [7]螺旋烯氰基酞菁（Zn - 7HPc），仅由两个同手性分子形成稳定的二聚体对。在四氢呋喃（THF）和二甲基亚砜（DMSO）中，二聚化常数分别估计高达8.96×10 M和3.42×10 M，表明二聚体具有显著的稳定性。此外，Zn - 7HPc表现出手性自分类行为，这也导致在消旋样品中优先形成同手性二聚体。如通过大的混合比例常数和对热力学稳定混合价态的IV - CT带的观察所揭示的，二聚体形式的两个酞菁亚基彼此强烈相互作用。
