TY - JOUR
T1 - TriQuinoline
AU - Adachi, Shinya
AU - Shibasaki, Masakatsu
AU - Kumagai, Naoya
N1 - Funding Information:
(TQ H+)n(1–2) was supported by NMR and ESI-TOF measurements and corroborated by computational calculations. The two-directional non-covalent interactions of TQ H+ enabled the construction of the ternary complex [12]CPP ⊃ (TQ H+/coronene), in which TQ serves as a liaison to assemble the inherently non-associative molecules [12]CPP and coronene. Moreover, the non-covalent interactions of water-miscible TQ H+ are also operative in aqueous media, as confirmed by intercalation assays. Despite their considerable structural similarity, the remarkable features of TQ are absent in DQ-Im, further highlighting the significant impact of the rigid 2D architecture of TQ. These intriguing properties are revealed by the strategic bottom-up synthesis of TQ as a discrete small molecular mimic for a defective graphitic sheet featuring pyridinic nitrogens, allowing for an in-depth understanding of its inherent physicochemical properties. Building up polymeric entities including TQ units as well as potential analogues with distinct defect sizes and topologies will provide more opportunity to identify hitherto unknown functional materials, and as such is currently underway in our laboratory.
Publisher Copyright:
© 2019, The Author(s).
PY - 2019/12/1
Y1 - 2019/12/1
N2 - 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.
AB - 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.
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U2 - 10.1038/s41467-019-11818-1
DO - 10.1038/s41467-019-11818-1
M3 - Article
C2 - 31444349
AN - SCOPUS:85071313660
SN - 2041-1723
VL - 10
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 3820
ER -