RESUMO
Two-dimensional covalent organic frameworks (COFs) are an emerging class of photocatalytic materials for solar energy conversion. In this work, we report a pair of structurally isomeric COFs with reversed imine bond directions, which leads to drastic differences in their physical properties, photophysical behaviors, and photocatalytic CO2 reduction performance after incorporating a Re(bpy)(CO)3Cl molecular catalyst through bipyridyl units on the COF backbone (Re-COF). Using the combination of ultrafast spectroscopy and theory, we attributed these differences to the polarized nature of the imine bond that imparts a preferential direction to intramolecular charge transfer (ICT) upon photoexcitation, where the bipyridyl unit acts as an electron acceptor in the forward imine case (f-COF) and as an electron donor in the reverse imine case (r-COF). These interactions ultimately lead the Re-f-COF isomer to function as an efficient CO2 reduction photocatalyst, while the Re-r-COF isomer shows minimal photocatalytic activity. These findings not only reveal the essential role linker chemistry plays in COF photophysical and photocatalytic properties but also offer a unique opportunity to design photosensitizers that can selectively direct charges.
RESUMO
The ligand-nanocrystal boundaries of colloidal quantum dots (QDs) mediate the primary energy and electron transfer processes that underpin photochemical and photocatalytic transformations at their surfaces. We use mid-infrared transient absorption spectroscopy to reveal the influence that ligand structure and bonding to nanocrystal surfaces have on the changes of the excited state surface chemistry of this boundary in PbS QDs and the corresponding impact on charge transfer processes between nanocrystals. We demonstrate that oleate ligands undergo marked changes in their bonding to surfaces in the excitonic excited states of the nanocrystals, indicating that oleate passivated PbS surfaces undergo significant structural changes following photoexcitation. These changes can impact the surface mobility of the ligands and the ability of redox shuttles to approach the nanocrystal surfaces to undergo charge transfer in photocatalytic reactions. In contrast, markedly different transient vibrational features are observed in iodide/mercaptoproprionic acid passivated PbS QD films that result from charge transfer between neighboring nanocrystals and localization of holes at the nanocrystal surfaces near MPA ligands. This ability to distinguish the influence that excitonic excited states vs charge transfer processes have on the surface chemistry of the ligand-nanocrystal boundary lays the groundwork for exploration of how this boundary can be understood and controlled for the design of nanocrystalline materials tailored for specific applications in solar energy harvesting and photocatalytic reactions.
RESUMO
We report strong coupling between light and polaron optical excitations in a doped organic semiconductor microcavity at room temperature. Codepositing MoO_{3} and the hole transport material 4, 4^{'}-cyclohexylidenebis[N, N-bis(4-methylphenyl)benzenamine] introduces a large hole density with a narrow linewidth optical transition centered at 1.8 eV and an absorption coefficient exceeding 10^{4} cm^{-1}. Coupling this transition to a Fabry-Pérot cavity mode yields upper and lower polaron polariton branches that are clearly resolved in angle-dependent reflectivity with a vacuum Rabi splitting âΩ_{R}>0.3 eV. This result establishes a path to electrically control polaritons in organic semiconductors and may lead to increased polariton-polariton Coulombic interactions that lower the threshold for nonlinear phenomena such as polariton condensation and lasing.
RESUMO
Ultrafast vibrational spectroscopy in the mid-infrared was used to directly probe the delocalization of excitons in two different perylenediimide (PDI) derivatives that are predicted to preclude the formation of excimers, which can act as trap sites for excited state energy in organic semiconductors. We identified vibrational modes within the conjugated C-C stretch modes of PDI molecules whose frequencies reported the interactions of molecules within delocalized excitonic states. The vibrational linewidths of these modes, which we call intermolecular coordinate coupled (ICC) modes, provided a direct probe of the extent of exciton delocalization among the PDI molecules, which was confirmed using X-ray diffraction and electro-absorption spectroscopy. We show that a slip-stacked geometry among the PDI molecules in their crystals promotes delocalized charge-transfer (CT) excitons, while localized Frenkel excitons tend to form in crystals with helical, columnar stacking geometries. Because all molecules possess vibrational modes, the use of ultrafast mid-infrared spectroscopy to measure ICC vibrational modes offers a new approach to examine exciton delocalization in a variety of small molecule electron acceptors for optoelectronic and organic photovoltaic applications.
RESUMO
The ligand shell around colloidal quantum dots mediates the electron and energy transfer processes that underpin their use in optoelectronic and photocatalytic applications. Here, we show that the surface chemistry of carboxylate anchoring groups of oleate ligands passivating PbS quantum dots undergoes significant changes when the quantum dots are excited to their excitonic states. We directly probe the changes of surface chemistry using time-resolved mid-infrared spectroscopy that records the evolution of the vibrational frequencies of carboxylate groups following excitation of the electronic states. The data reveal a reduction of the Pb-O coordination of carboxylate anchoring groups to lead atoms at the quantum dot surfaces. The dynamic surface chemistry of the ligands may increase their surface mobility in the excited state and enhance the ability of molecular species to penetrate the ligand shell to undergo energy and charge transfer processes that depend sensitively on distance.
RESUMO
Observations of the hot-phonon bottleneck, which is predicted to slow the rate of hot carrier cooling in quantum confined nanocrystals, have been limited to date for reasons that are not fully understood. We used time-resolved infrared spectroscopy to directly measure higher energy intraband transitions in PbS colloidal quantum dots. Direct measurements of these intraband transitions permitted detailed analysis of the electronic overlap of the quantum confined states that may influence their relaxation processes. In smaller PbS nanocrystals, where the hot-phonon bottleneck is expected to be most pronounced, we found that relaxation of parity selection rules combined with stronger electron-phonon coupling led to greater spectral overlap of transitions among the quantum confined states. This created pathways for fast energy transfer and relaxation that may bypass the predicted hot-phonon bottleneck. In contrast, larger, but still quantum confined nanocrystals did not exhibit such relaxation of the parity selection rules and possessed narrower intraband states. These observations were consistent with slower relaxation dynamics that have been measured in larger quantum confined systems. These findings indicated that, at small radii, electron-phonon interactions overcome the advantageous increase in energetic separation of the electronic states for PbS quantum dots. Selection of appropriately sized quantum dots, which minimize spectral broadening due to electron-phonon interactions while maximizing electronic state separation, is necessary to observe the hot-phonon bottleneck. Such optimization may provide a framework for achieving efficient hot carrier collection and multiple exciton generation.
RESUMO
Ultrafast vibrational spectroscopy in the mid-infrared spectral range provides the opportunity to probe the dynamics of electronic states involved in all stages of the singlet fission reaction through their unique vibrational frequencies. This capability is demonstrated using a model singlet fission chromophore, 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn). The alkyne groups of the TIPS side chains are coupled to the conjugated framework of the pentacene cores, enabling direct examination of the dynamics of triplet excitons that have successfully separated from correlated triplet pair states in crystalline films of TIPS-Pn. Relaxation processes during the separation of triplet excitons and triplet-triplet annihilation after their separation result in the formation of hot ground state molecules that also exhibit unique vibrational frequencies. Because all organic molecules possess native vibrational modes, ultrafast vibrational spectroscopy offers a new approach to examine the dynamics of electronic intermediates that may inform ongoing efforts to utilize singlet fission to overcome thermalization losses in photovoltaic applications.