π‑Extended Helical Multilayer Nanographenes with Layer-Dependent Chiroptical Properties

• Published in: Journal of the American Chemical Society 2023-12, Vol.145 (49), p.26824-26832
• Main Authors: Niu, Wenhui, Fu, Yubin, Qiu, Zhen-Lin, Schürmann, Christian J., Obermann, Sebastian, Liu, Fupin, Popov, Alexey A., Komber, Hartmut, Ma, Ji, Feng, Xinliang
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.3c09350

Helical nanographenes (NGs) have attracted increasing attention recently because of their intrinsic chirality and exotic chiroptical properties. However, the efficient synthesis of extended helical NGs featuring a multilayer topology is still underdeveloped, and their layer-dependent chiroptical properties remain elusive. In this study, we demonstrate a modular synthetic strategy to construct a series of novel helical NGs (1–3) with a multilayer topology through a consecutive Diels–Alder reaction and regioselective cyclodehydrogenation from the readily accessible phenanthrene-based precursors bearing ethynyl groups. The resultant NGs exhibit bilayer, trilayer, and tetralayer structures with elongated π extension and rigid helical backbones, as unambiguously confirmed by single-crystal X-ray or electron diffraction analysis. We find that the photophysical properties of these helical NGs are notably influenced by the degree of π extension, which varies with the number of layers, leading to obvious redshifted absorption, a fast rising molar extinction coefficient (ε), and markedly boosted fluorescence quantum yield (Φf). Moreover, the embedded [7]­helicene subunits in these NGs result in stable chirality, enabling both chiral resolution and exploration of their layer-dependent chiroptical properties. Profiting from the good alignment of electric and magnetic dipole moments determined by the multilayer structure, the resultant NGs exhibit excellent circular dichroism and circularly polarized luminescence response with unprecedented high CPL brightness up to 168 M–1 cm–1, rendering them promising candidates for CPL emitters.