Organisch-Chemisches Institut, Westfälische-Wilhelms Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
Institut für Physikalische Chemie, Westfälische-Wilhelms Universität Münster, Corrensstraße 28/30, 48149, Münster, Germany.
Angew Chem Int Ed Engl. 2019 Aug 12;58(33):11344-11349. doi: 10.1002/anie.201905064. Epub 2019 Jul 4.
Controlling the nanoscale morphology in assemblies of π-conjugated molecules is key to developing supramolecular functional materials. Here, we report an unsymmetrically substituted amphiphilic Pt complex 1 that shows unique self-assembly behavior in nonpolar media, providing two competing anti-cooperative and cooperative pathways with distinct molecular arrangement (long- vs. medium-slipped, respectively) and nanoscale morphology (discs vs. fibers, respectively). With a thermodynamic model, we unravel the competition between the anti-cooperative and cooperative pathways: buffering of monomers into small-sized, anti-cooperative species affects the formation of elongated assemblies, which might open up new strategies for pathway control in self-assembly. Our findings reveal that side-chain immiscibility is an efficient method to control anti-cooperative assemblies and pathway complexity in general.
控制π共轭分子组装体中的纳米形貌是开发超分子功能材料的关键。在这里，我们报告了一种不对称取代的两亲性 Pt 配合物 1，它在非极性介质中表现出独特的自组装行为，提供了两种具有不同分子排列（分别为长滑移和中滑移）和纳米形貌（分别为盘状和纤维状）的竞争反协同和协同途径。通过热力学模型，我们揭示了反协同和协同途径之间的竞争：单体缓冲成小尺寸的反协同物种会影响长链组装的形成，这可能为自组装中的途径控制开辟新的策略。我们的发现表明，侧链不混溶性是控制反协同组装体和一般途径复杂性的有效方法。
