2026 Volume 87 Pages 32-40
This account summarizes our systematic development of rigid π-conjugated dendrimers as precisely synthetic platforms that enable functions inaccessible to conventional linear polymers. By focusing on the intrinsic geometric density gradient of dendritic architectures, we designed phenylazomethine dendrimers (DPAs) that generate well-defined intramolecular electronic and potential gradients. These gradients drive a unique stepwise metal ion coordination behavior, allowing metal ions to be accumulated in a highly ordered manner with atomic-level precision. Building on this concept, we established the “atom-hybridization” which enables the synthesis of subnanometer metal and alloy clusters with strictly defined atomic counts and compositions, including multi-element subnano alloy particles and superatoms. Such atomically precise subnano particles exhibit unprecedented atom-number-dependent catalytic activities, strong alloy effects, and low-temperature reactivity beyond the scope of conventional nanoparticles. Furthermore, the rigid dendritic framework provides stable internal nanospaces that support enzyme-like molecular shape recognition, induced-fit catalysis, and long-lived charge-separated states driven by designed potential gradients. Together, these studies establish dendrimers as a versatile molecular platform that bridges polymer chemistry, coordination chemistry, catalysis, and quantum materials science, offering a general strategy for designing functional materials based on atomic-scale control.
