Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747AG Groningen, The Netherlands.
Phys Chem Chem Phys. 2020 May 13;22(18):10179-10188. doi: 10.1039/d0cp01734e.
The bottom-up fabrication of functional nanosystems for light-harvesting applications and excitonic devices often relies on molecular self-assembly. Gaining access to the intermediate species involved in self-assembly would provide valuable insights into the pathways via which the final architecture has evolved, yet difficult to achieve due to their intrinsically short-lived nature. Here, we employ a lab-on-a-chip approach as a means to obtain in situ control of the structural complexity of an artificial light-harvesting complex: molecular double-walled nanotubes. Rapid and stable dissolution of the outer wall was realized via microfluidic mixing thereby rendering the thermodynamically unstable inner tubes accessible to spectroscopy. By measurement of the linear dichroism and time-resolved photoluminescence of both double-walled nanotubes and isolated inner tubes we show that the optical (excitonic) properties of the inner tube are remarkably robust to such drastic perturbation of the system's supramolecular structure as removal of the outer wall. The developed platform is readily extendable to a broad range of practical applications such as e.g. self-assembling systems and molecular photonics devices.
用于光捕获应用和激子器件的功能纳米系统的自下而上制造通常依赖于分子自组装。获得参与自组装的中间物种将为最终结构演变的途径提供有价值的见解，但由于它们固有的短寿命性质，很难实现。在这里，我们采用芯片上实验室的方法来获得对人工光捕获复合物的结构复杂性的原位控制：分子双层纳米管。通过微流混合实现了外壁的快速和稳定溶解，从而使热力学上不稳定的内管能够进行光谱测量。通过测量双层纳米管和分离的内管的线二色性和时间分辨光致发光，我们表明内管的光学（激子）性质对内管的超分子结构的这种剧烈扰动具有很强的稳定性，例如去除外壁。所开发的平台可轻松扩展到广泛的实际应用，例如例如自组装系统和分子光子学器件。
