Photophysics of graphene quantum dot assemblies with axially coordinated cobaloxime catalysts

Singh, Varun; Gupta, Nikita; Hargenrader, George N.; Askins, Erik J.; Valentine, Andrew S.; Kumar, Gaurav; Mara, Michael W.; Agarwal, Neeraj; Li, Xiaosong; Chen, Lin X.; Cordones, Amy A.; Glusac, Ksenija D.

doi:10.1063/5.0018581

Photophysics of graphene quantum dot assemblies with axially coordinated cobaloxime catalysts

Journal Article · Mon Sep 28 00:00:00 EDT 2020 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0018581· OSTI ID:1775446

^[1]; ^[1]; Hargenrader, George N. ^[1]; ^[1]; ^[2]; ^[3]; ^[4]; ^[5]; ^[2]; ^[4]; ^[3]; ^[1]

Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Washington, Seattle, WA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
Univ. of Mumbai (India)

We report a study of chromophore-catalyst assemblies composed of light harvesting hexabenzocoronene (HBC) chromophores axially coordinated to two cobaloxime complexes. The chromophore-catalyst assemblies were prepared using bottom-up synthetic methodology and characterized using solid-state NMR, IR, and x-ray absorption spectroscopy. Detailed steady-state and time-resolved laser spectroscopy was utilized to identify the photophysical properties of the assemblies, coupled with time-dependent DFT calculations to characterize the relevant excited states. The HBC chromophores tend to assemble into aggregates that exhibit high exciton diffusion length (D = 18.5 molecule²/ps), indicating that over 50 chromophores can be sampled within their excited state lifetime. We find that the axial coordination of cobaloximes leads to a significant reduction in the excited state lifetime of the HBC moiety, and this finding was discussed in terms of possible electron and energy transfer pathways. By comparing the experimental quenching rate constant (1.0 × 10⁹ s^-1) with the rate constant estimates for Marcus electron transfer (5.7 × 10⁸ s^-1) and Förster/Dexter energy transfers (8.1 × 10⁶ s^-1 and 1.0 × 10¹⁰ s^-1), we conclude that both Dexter energy and Marcus electron transfer process are possible deactivation pathways in CoQD-A. No charge transfer or energy transfer intermediate was detected in transient absorption spectroscopy, indicating fast, subpicosecond return to the ground state. Finally, these results provide important insights into the factors that control the photophysical properties of photocatalytic chromophore-catalyst assemblies.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-06CH11357; AC02-76SF00515

OSTI ID:: 1775446

Alternate ID(s):: OSTI ID: 1668104

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 12 Vol. 153; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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