Planar Chiral Charge‐Transfer Cyclophanes: Convenient Synthesis, Circularly Polarized Light‐Responsive Photothermal Conversion and Supramolecular Chiral Assembly

• Published in: Angewandte Chemie 2024-11
• Main Authors: Wang, Zhengyan, Liu, Yiping, Quan, Xiuni, Zhang, Wenxuan, Tan, Renjun, Gu, Hao, Sheng, Chunqi, Duan, Chunbo, Xing, Pengyao, Wan, Jun‐Hua
• Format: Article
• Language: English
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202413295

We report herein a series of macrocycles in which the densely π‐stacked charge‐transfer (CT) donor/acceptor with naphthalenediimides (NDIs) or perylene diimide (PDI) as acceptor moiety pairing various donor moieties are locked by covalent bond. The X‐ray crystallography of C8BDT‐NDI reveals a short intramolecular π‐stacking distance around 3.4 Å and the existence of intermolecular donor/acceptor π‐stacking (3.7 Å). The intramolecular CT is highly dependent on the electron‐donating ability of donor moiety and replacing carbazole ( C8KZ ) with benzo[1,2‐b:4,5‐b′]dithiophene ( C8BDT ) or dihydroindolo[3,2‐b]indole ( C8DN ) redshift CT absorption into NIR region. Notably, both C8BDT‐NDI and C8DN‐NDI demonstrate excellent photothermal performance, which is a result of the active non‐radiative pathways. Interestingly, the different molecular symmetry between donor and acceptor moiety in cyclophanes endow C8BDT‐NDI and C8DN‐NDI with intrinsic planar chirality. The enantiomeric C8BDT‐NDI shows chiral selectivity for incident light, i.e., when irradiated by left‐circularly polarized light, ( R)‐ C8BDT‐NDI is more sensitive and a higher maximum stable temperature is achieved. While, enantiomeric C8DN‐NDI pack with different orientations forming M‐ and P ‐handedness helix, respectively, demonstrating molecular planar chirality being transferred and amplified through molecular assembly. These results provide insight into the intramolecular charge transfer in enforced D/A π‐stacks in which CT interactions and planar chirality would be engineered through structural control.