TY - JOUR
T1 - Impact of pyrene orientation on the electronic properties and stability of graphene ribbons
AU - Smith, Tanner
AU - Thorley, Karl
AU - Dimmitt, Kevin
AU - Parkin, Sean
AU - Ostroverkhova, Oksana
AU - Anthony, John
N1 - Publisher Copyright:
© 2024 The Royal Society of Chemistry.
PY - 2024/9/18
Y1 - 2024/9/18
N2 - We report the synthesis and study of trialkylsilylethyne-substituted “oblique” pyrene-fused acenes, carbon nanoribbons demonstrating near-IR absorption with reversible oxidation and reduction, and acene-like evolution of electronic properties upon extension of the aromatic core. Their electronic structures are investigated through DFT studies, which support the more delocalized nature of their frontier molecular orbitals compared to more common “vertical” pyrene systems. Despite a longer aromatic core, the more extended of the two examples demonstrates enhanced photostability compared to the shorter derivative, running counter to the trend in linear acenes. The unusual stability of the longer core is ultimately linked to its relatively low T1 energy inhibiting the generation of reactive O2 species. The byproduct generated upon photooxidation of the shorter nanoribbon appears to catalyze the generation of 1O2 due to its large T1 energy, leading to its relatively decreased stability.
AB - We report the synthesis and study of trialkylsilylethyne-substituted “oblique” pyrene-fused acenes, carbon nanoribbons demonstrating near-IR absorption with reversible oxidation and reduction, and acene-like evolution of electronic properties upon extension of the aromatic core. Their electronic structures are investigated through DFT studies, which support the more delocalized nature of their frontier molecular orbitals compared to more common “vertical” pyrene systems. Despite a longer aromatic core, the more extended of the two examples demonstrates enhanced photostability compared to the shorter derivative, running counter to the trend in linear acenes. The unusual stability of the longer core is ultimately linked to its relatively low T1 energy inhibiting the generation of reactive O2 species. The byproduct generated upon photooxidation of the shorter nanoribbon appears to catalyze the generation of 1O2 due to its large T1 energy, leading to its relatively decreased stability.
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U2 - 10.1039/d4tc03072a
DO - 10.1039/d4tc03072a
M3 - Article
AN - SCOPUS:85204362262
SN - 2050-7526
VL - 12
SP - 14816
EP - 14822
JO - Journal of Materials Chemistry C
JF - Journal of Materials Chemistry C
IS - 37
ER -