Institute of Microbial Chemistry, 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo, 141-0021, Japan.
Nat Commun. 2019 Aug 23;10(1):3820. doi: 10.1038/s41467-019-11818-1.
The bottom-up synthesis of structurally well-defined motifs of graphitic materials is crucial to understanding their physicochemical properties and to elicit new functions. Herein, we report the design and synthesis of TriQuinoline (TQ) as a molecular model for pyridinic-nitrogen defects in graphene sheets. TQ is a trimer of quinoline units concatenated at the 2- and 8-positions in a head-to-tail fashion, whose structure leads to unusual aromatisation behaviour at the final stage of the synthesis. The central atomic-sized void endows TQ with high proton affinity, which was confirmed empirically and computationally. TQ•H is a two-dimensional cationic molecule that displays both π-π and CH-π contact modes, culminating in the formation of the ternary complex ([12]cycloparaphenylene(CPP) ⊃ (TQ•H/coronene)) that consists of TQ•H, coronene (flat), and [12]cycloparaphenylene ([12]CPP) (ring). The water-miscibility of TQ•H allows it to serve as an efficient DNA intercalator for e.g. the inhibition of topoisomerase I activity.
自下而上合成结构明确的石墨材料基元对于理解其物理化学性质和引出新功能至关重要。在此，我们报告了 TriQuinoline（TQ）的设计和合成，TQ 是一种在 2-和 8-位以头尾方式连接的喹啉单元三聚体，其结构导致在合成的最后阶段出现异常的芳香化行为。中央原子大小的空隙赋予 TQ 高质子亲和力，这一点通过经验和计算得到了证实。TQ•H 是一种二维阳离子分子，显示出π-π 和 CH-π 接触模式，最终形成三元配合物([12]cycloparaphenylene(CPP)⊃(TQ•H/coronene))，其中包含 TQ•H、coronene（平面）和[12]cycloparaphenylene([12]CPP)（环）。TQ•H 的水溶性使其可用作有效的 DNA 嵌入剂，例如抑制拓扑异构酶 I 活性。
