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Resolving Site-Specific Energy Levels of Small-Molecule Donor-Acceptor Heterostructures Close to Metal Contacts.

ABSTRACT: The active material of optoelectronic devices must accommodate for contacts which serve to collect or inject the charge carriers. It is the purpose of this work to find out to which extent properties of organic optoelectronic layers change close to metal contacts compared to known properties of bulk materials. Bottom-up fabrication capabilities of model interfaces under ultrahigh vacuum and single-atom low temperature (LT)-STM spectroscopy with density functional theory (DFT) calculations are used to detect the spatial modifications of electronic states such as frontier-orbitals at interfaces. The system under consideration is made of a silver substrate covered with a blend of C₆₀ and ZnPc molecules of a few monolayers. When C₆₀ and ZnPc are separately adsorbed on Ag(111), they show distinct spectroscopic features in STM. However, when C₆₀ is added to the ZnPc monolayer, it shows scanning tunneling spectra similar to ZnPc, revealing a strong interaction of C₆₀ with the ZnPc induced by the substrate. DFT calculations on a model complex confirm the strong hybridization of C₆₀ with ZnPc layer upon adsorption on Ag(111), thus highlighting the role of boundary layers where the donor-acceptor character is strongly perturbed. The calculation also reveals a significant charge transfer from the Ag to the complex that is likely responsible for a downward shift of the molecular LUMO in agreement with the experiment.

SUBMITTER: Benhnia A

PROVIDER: S-EPMC8234413 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Photoreduction of fullerene and the consequent stabilisation of a charge-separated state in a donor-acceptor assembly have been achieved, overcoming the common problem of a fullerene-based triplet state being an energy sink that prevents charge-separation. A route to incorporate a C60-fullerene electron acceptor moiety into a catecholate-Pt(ii)-diimine photoactive dyad, which contains an unusually strong electron donor, 3,5-di-tert-butylcatecholate, has been developed. The synthetic methodology is based on the formation of the aldehyde functionalised bipyridine-Pt(ii)-3,5-di-tert-butylcatechol dyad which is then added to the fullerene cage via a Prato cycloaddition reaction. The resultant product is the first example of a fullerene-diimine-Pt-catecholate donor-acceptor triad, C60bpy-Pt-cat. The triad exhibits an intense solvatochromic absorption band in the visible region due to catechol-to-diimine charge-transfer, which, together with fullerene-based transitions, provides efficient and tuneable light harvesting of the majority of the UV/visible spectral range. Cyclic voltammetry, EPR and UV/vis/IR spectroelectrochemistry reveal redox behaviour with a wealth of reversible reduction and oxidation processes forming multiply charged species and storing multiple redox equivalents. Ultrafast transient absorption and time resolved infrared spectroscopy, supported by molecular modelling, reveal the formation of a charge-separated state [C60?-bpy-Pt-cat?+] with a lifetime of ?890 ps. The formation of cat?+ in the excited state is evidenced directly by characteristic absorption bands in the 400-500 nm region, while the formation of C60?- was confirmed directly by time-resolved infrared spectroscopy, TRIR. An IR-spectroelectrochemical study of the mono-reduced building block (C60-bpy)PtCl2, revealed a characteristic C60?- vibrational feature at 1530 cm-1, which was also detected in the TRIR spectra. This combination of experiments offers the first direct IR-identification of C60?- species in solution, and paves the way towards the application of transient infrared spectroscopy to the study of light-induced charge-separation in C60-containing assemblies, as well as fullerene films and fullerene/polymer blends in various OPV devices. Identification of the unique vibrational signature of a C60-anion provides a new way to follow photoinduced processes in fullerene-containing assemblies by means of time-resolved vibrational spectroscopy, as demonstrated for the fullerene-transition metal chromophore assembly with the lowest energy charge-separated excited state.

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Resolving Site-Specific Energy Levels of Small-Molecule Donor-Acceptor Heterostructures Close to Metal Contacts.

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