Long-Lived Excited State in a Solubilized Graphene Nanoribbon

Graphene nanoribbons have excellent light-absorbing properties but often exhibit short excited-state lifetimes that prevent their applications in photocatalysis. Here, we report a long-lived charge-transfer triplet excited state in a well-solubilized, chlorinated graphene nanoribbon (Cl-GNR) with edges modified by bipyrimidine (bpm) moieties. The photophysical behavior of Cl-GNR was observed and characterized by steady-state UV-vis absorption and emission spectroscopy, transient absorption spectroscopy on the ps-ms timescale, and density functional theory (DFT) calculations. Both the Cl-GNR and its monomeric subunit, chlorinated graphene quantum dot (Cl-GQD), were synthesized using bottom-up techniques to produce the H-analogs of the compounds followed by edge-chlorination to achieve soluble products. The absorption spectra of Cl-GQD and Cl-GNR appear in the UV-vis range with lowest-energy peaks at 375 and 600 nm, respectively. The excitons in Cl-GNR were found to exhibit charge-transfer character with the bpm edges serving as electron acceptors. DFT calculations indicate that the excitons are relatively localized, spreading over at most two monomeric units of the GNR. Transient absorption spectroscopy shows that singlet excited states of Cl-GQD and Cl-GNR undergo intersystem crossing with similar to 300 ps lifetime to form triplet states that last for 15.7 mu s (Cl-GQD) and 106 mu s (Cl-GNR). These properties, combined with the ability of the bpm sites to coordinate transition metals, make Cl-GNRs promising light-harvesting motifs for photocatalytic applications.