Synthesis of N = 8 Armchair Graphene Nanoribbons from Four Distinct Polydiacetylenes

We demonstrate a highly efficient thermal conversion of four differently substituted polydiacetylenes (PDAs 1 and 2a–c) into virtually indistinguishable N = 8 armchair graphene nanoribbons ([8]AGNR). PDAs 1 and 2a–c are themselves easily accessed through photochemically initiated topochemical polyme...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Journal of the American Chemical Society 2017-11, Vol.139 (44), p.15878-15890
Hauptverfasser: Jordan, Robert S, Li, Yolanda L, Lin, Cheng-Wei, McCurdy, Ryan D, Lin, Janice B, Brosmer, Jonathan L, Marsh, Kristofer L, Khan, Saeed I, Houk, K. N, Kaner, Richard B, Rubin, Yves
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:We demonstrate a highly efficient thermal conversion of four differently substituted polydiacetylenes (PDAs 1 and 2a–c) into virtually indistinguishable N = 8 armchair graphene nanoribbons ([8]AGNR). PDAs 1 and 2a–c are themselves easily accessed through photochemically initiated topochemical polymerization of diynes 3 and 4a–c in the crystal. The clean, quantitative transformation of PDAs 1 and 2a–c into [8]AGNR occurs via a series of Hopf pericyclic reactions, followed by aromatization reactions of the annulated polycyclic aromatic intermediates, as well as homolytic bond fragmentation of the edge functional groups upon heating up to 600 °C under an inert atmosphere. We characterize the different steps of both processes using complementary spectroscopic techniques (CP/MAS 13C NMR, Raman, FT-IR, and XPS) and high-resolution transmission electron microscopy (HRTEM). This novel approach to GNRs exploits the power of crystal engineering and solid-state reactions by targeting very large organic structures through programmed chemical transformations. It also affords the first reported [8]AGNR, which can now be synthesized on a large scale via two operationally simple and discrete solid-state processes.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.7b08800