Ultrafast Events of Photoexcited Iron(III) Chloride for Activation of Benzylic C-H Bonds.

The usage of rare-earth-metal catalysts in the synthesis of organic compounds is widespread in chemical industries but is limited owing to its environmental and economic costs. However, recent studies indicate that abundant-earth metals like iron(III) chloride can photocatalyze diverse organic transformations using blue-light LEDs. Still, the underlying mechanism behind such activity is debatable and controversial, especially in the absence of ultrafast spectroscopic results. To address this urgent challenge, we performed femtosecond time-resolved electronic absorption spectroscopy experiments of iron(III) chloride in selected organic solvents relevant to its photocatalytic applications. Our results show that the long-lived species [Fe(II) ← Cl•]* is primarily responsible for both oxidizing the organic substrate and reducing molecular oxygen through the diffusion process, leading to the final product and regenerating the photocatalyst rather than the most widely proposed free chloride radical (Cl•). Our study will guide the rational design of efficient earth-abundant photocatalysts.

Multi-spectroscopic study of electrochemically-formed oxide-derived gold electrodes.

Oxide-derived metals are produced by reducing an oxide precursor. These materials, including gold, have shown improved catalytic performance over many native metals. The origin of this improvement for gold is not yet understood. In this study, operando non-resonant sum frequency generation (SFG) and ex situ high-pressure X-ray photoelectron spectroscopy (HP-XPS) have been employed to investigate electrochemically-formed oxide-derived gold (OD-Au) from polycrystalline gold surfaces. A range of different oxidizing conditions were used to form OD-Au in acidic aqueous medium (H3PO4, pH = 1). Our electrochemical data after OD-Au is generated suggest that the surface is metallic gold, however SFG signal variations indicate the presence of subsurface gold oxide remnants between the metallic gold surface layer and bulk gold. The HP-XPS results suggest that this subsurface gold oxide could be in the form of Au2O3 or Au(OH)3. Furthermore, the SFG measurements show that with reducing electrochemical treatments the original gold metallic state can be restored, meaning the subsurface gold oxide is released. This work demonstrates that remnants of gold oxide persist beneath the topmost gold layer when the OD-Au is created, potentially facilitating the understanding of the improved catalytic properties of OD-Au.

Charge Transfer Process of a Solvated Hydrogen-Bonded Organic Network.

We show the first example of an organic linker (OL) terminated by carboxylic groups that can form a hydrogen-bonded network/polymer (HBN) in solution under controlled conditions in which the photogenerated charges can hop from a monomer OL to the hydrogen-bonded backbone of OLs, as probed by transient absorption (fs-TA). While fs-TA reveals a slow twisting process in the monomer form of the OL, the formation of a hydrogen-bonded network in solution suppresses such process and favors instead a charge transfer (CT) state along the low-lying hydrogen-bonded backbone. Theoretical calculations show that such solvated HBN in a specific polar solvent is stabilized due to the huge change of the dipole moment from monomer compared to the network, leading to a charge delocalization character due to the symmetry breaking. Our findings will open new avenues for implementing solvated hydrogen-bonded molecules in applications such as sensing and photocatalysis.

Ultrafast transient infrared spectroscopy for probing trapping states in hybrid perovskite films.

Studying the charge dynamics of perovskite materials is a crucial step to understand the outstanding performance of these materials in various fields. Herein, we utilize transient absorption in the mid-infrared region, where solely electron signatures in the conduction bands are monitored without external contributions from other dynamical species. Within the measured range of 4000 nm to 6000 nm (2500-1666 cm-1), the recombination and the trapping processes of the excited carriers could be easily monitored. Moreover, we reveal that within this spectral region the trapping process could be distinguished from recombination process, in which the iodide-based films show more tendencies to trap the excited electrons in comparison to the bromide-based derivatives. The trapping process was assigned due to the emission released in the mid-infrared region, while the traditional band-gap recombination process did not show such process. Various parameters have been tested such as film composition, excitation dependence and the probing wavelength. This study opens new frontiers for the transient mid-infrared absorption to assign the trapping process in perovskite films both qualitatively and quantitatively, along with the potential applications of perovskite films in the mid-IR region.

Spin-Orbit Charge-Transfer Intersystem Crossing of Compact Naphthalenediimide-Carbazole Electron-Donor-Acceptor Triads.

Compact electron donor-acceptor triads based on carbazole (Cz) and naphthalenediimide (NDI) were prepared to study the spin-orbit charge-transfer intersystem crossing (SOCT-ISC). By variation of the molecular conformation and electron-donating ability of the carbazole moieties, the electronic coupling between the two units was tuned, and as a result charge-transfer (CT) absorption bands with different magnitudes were observed (ε = 4000-18 000 M-1 cm-1). Interestingly, the triads with NDI attached at the 3-C position or with a phenyl spacer at the N position of the Cz moiety, thermally activated delayed fluorescence (TADF) was observed. Femtosecond transient absorption (fs-TA) spectroscopy indicated fast electron transfer (0.8-1.5 ps) from the Cz to NDI unit, followed by population of the triplet state (150-600 ps). Long-lived triplet states (up to τT = 45-50 µs) were observed for the triads. The solvent-polarity-dependent singlet-oxygen quantum yield (ΦΔ) is 0-26%. Time-resolved electron paramagnetic resonance (TREPR) spectral study of TADF molecules indicated the presence of the 3CT state for NDI-Cz-Ph (zero-field-splitting parameter D = 21 G) and an 3LE state for NDI-Ph-Cz (D = 586 G). The triads were used as triplet photosensitizers in triplet-triplet annihilation upconversion by excitation into the CT absorption band; the upconversion quantum yield was ΦUC = 8.2%, and there was a large anti-Stokes shift of 0.55 eV. Spatially confined photoexcitation is achieved with the upconversion using focusing laser beam excitation, and not the normally used collimated laser beam, i.e., the upconversion was only observed at the focal point of the laser beam. Photo-driven intermolecular electron transfer was demonstrated with reversible formation of the NDI-• radical anion in the presence of the sacrificial electron donor triethanolamine.

Highly Emissive Biological Bilirubin Molecules: Shedding New Light on the Phototherapy Scheme.

Bilirubin (BR) is the main end-product of the hemoglobin catabolism. For decades, its photophysics has been mainly discussed in terms of ultrafast deactivation of the excited state in solution, where, indeed, BR shows a very low green emission quantum yield (EQY), 0.03%, resulting from an efficient nonradiative isomerization process. Herein, we present, for the first time, unique and exceptional photophysical properties of solid-state BR, which amend by changing the type of crystal, from a closely packed α crystal to an amorphous loosely packed ß crystal. BR α crystals show a very bright red emission with an EQY of ca. 24%, whereas ß crystals present, in addition, a low green EQY of ca. 0.5%. By combining density functional theory (DFT) calculations and time-resolved emission spectroscopy, we trace back this dual emission to the presence of two types of BR molecules in the crystal: a "stiff" monomer, M1, distorted by particularly strong internal H-bonds and a "floppy" monomer, M2, having a structure close to that of BR in solution. We assign the red strong emission of BR crystals to M1 present in both the α and ß crystals, while the low green emission, only present in the amorphous (ß) crystal, is interpreted as M2 emission. Efficient energy-transfer processes from M2 to M1 in the closely packed α crystal are invoked to explain the absence of the green component in its emission spectrum. Interestingly, these unique photophysical properties of BR remain in polar solvents such as water. Based on these unprecedented findings, we propose a new model for the phototherapy scheme of BR inside the human body and highlight the usefulness of BR as a strong biological fluorescent probe.

Twisted Intramolecular Charge Transfer (TICT) Controlled by Dimerization: An Overlooked Piece of the TICT Puzzle.

Organic dyes have shown high efficiencies in solar cells, which is mainly attributed to the push-pull strategy present in such dyes upon attaching to the semiconductor surfaces. We deeply studied the fundamental photophysical properties of cyanoacrylic dyes, mostly the L1 dye, and found unique emission properties that depend on many factors such as the solvent polarity and the concentration of the dye and could present a complete emission picture about this family of dyes. The L1 dye shows an intramolecular charge transfer (ICT) emission state at low concentrations (approximately nanomolar scale) and shows a twisted intramolecular charge transfer (TICT) emission state in specific solvents upon increasing the concentration to the micromolar scale. Moreover, the associated emission lifetimes of the ICT and TICT states of the L1 dye depend on solvent basicity, highlighting the role of hydrogen bond formation on controlling such states. Density functional theory calculations are performed to gain insight into the photophysical properties of the dye and revealed that H-bonding between the carboxylic groups triggers the dimerization at low concentrations. Using femtosecond transient absorption, we assigned the rate of TICT formation to be in the range (160-650 fs)-1, depending on the size of the studied cyanoacrylic dye. Therefore, we add herein a new dimension for controlling the formation of the TICT state, in addition to the solvent polarity and acceptor strength parameters. These findings are not limited to the studied dyes, and we expect that numerous organic carboxylic acids dyes show similar properties.

Critical Role of Protons for Emission Quenching of Indoline Dyes in Solution and on Semiconductor Surfaces.

By combining time-correlated single photon counting (TCSPC) measurements, density functional theory (DFT), and time-dependent DFT (TD-DFT) calculations, we herein investigate the role of protons, in solutions and on semiconductor surfaces, for the emission quenching of indoline dyes. We show that the rhodanine acceptor moieties, and in particular the carbonyl oxygens, undergo protonation, leading to nonradiative excited-state deactivation. The presence of the carboxylic acid anchoring group, close to the rhodanine moiety, further facilitates the emission quenching, by establishing stable H-bond complexes with carboxylic acid quenchers, with high association constants, in both ground and excited states. This complexation favors the proton transfer process, at a low quencher concentration, in two ways: bringing close to the rhodanine unit the quencher and assisting the proton release from the acid by a partial-concerted proton donation from the close-by carboxylic group to the deprotonated acid. Esterification of the carboxylic group, indeed, inhibits the ground-state complex formation with carboxylic acids and thus the quenching at a low quencher concentration. However, the rhodanine moiety in the ester form can still be the source of emission quenching through dynamic quenching mechanism with higher concentrations of protic solvents or carboxylic acids. Investigating this quenching process on mesoporous ZrO2, for solar cell applications, also reveals the sensitivity of the adsorbed excited rhodanine dyes toward adsorbed protons on surfaces. This has been confirmed by using an organic base to remove surface protons and utilizing cynao-acrylic dye as a reference dye. Our study highlights the impact of selecting such acceptor group in the structural design of organic dyes for solar cell applications and the overlooked role of protons to quench the excited state for such chemical structures.

Elucidation of the Intersystem Crossing Mechanism in a Helical BODIPY for Low-Dose Photodynamic Therapy.

Intersystem crossing (ISC) of triplet photosensitizers is a vital process for fundamental photochemistry and photodynamic therapy (PDT). Herein, we report the co-existence of efficient ISC and long triplet excited lifetime in a heavy atom-free bodipy helicene molecule. Via theoretical computation and time-resolved EPR spectroscopy, we confirmed that the ISC of the bodipy results from its twisted molecular structure and reduced symmetry. The twisted bodipy shows intense long wavelength absorption (ϵ=1.76×105 m-1 cm-1 at 630 nm), satisfactory triplet quantum yield (ΦT =52 %), and long-lived triplet state (τT =492 µs), leading to unprecedented performance as a triplet photosensitizer for PDT. Moreover, nanoparticles constructed with such helical bodipy show efficient PDT-mediated antitumor immunity amplification with an ultra-low dose (0.25 µg kg-1 ), which is several hundred times lower than that of the existing PDT reagents.

Long-Lived Charge-Transfer State Induced by Spin-Orbit Charge Transfer Intersystem Crossing (SOCT-ISC) in a Compact Spiro Electron Donor/Acceptor Dyad.

We prepared conceptually novel, fully rigid, spiro compact electron donor (Rhodamine B, lactam form, RB)/acceptor (naphthalimide; NI) orthogonal dyad to attain the long-lived triplet charge-transfer (3 CT) state, based on the electron spin control using spin-orbit charge transfer intersystem crossing (SOCT-ISC). Transient absorption (TA) spectra indicate the first charge separation (CS) takes place within 2.5 ps, subsequent SOCT-ISC takes 8 ns to produce the 3 NI* state. Then the slow secondary CS (125 ns) gives the long-lived 3 CT state (0.94 µs in deaerated n-hexane) with high energy level (ca. 2.12 eV). The cascade photophysical processes of the dyad upon photoexcitation are summarized as 1 NI*→1 CT→3 NI*→3 CT. With time-resolved electron paramagnetic resonance (TREPR) spectra, an EEEAAA electron-spin polarization pattern was observed for the naphthalimide-localized triplet state. Our spiro compact dyad structure and the electron spin-control approach is different to previous methods for which invoking transition-metal coordination or chromophores with intrinsic ISC ability is mandatory.

Facile and noninvasive passivation, doping and chemical tuning of macroscopic hybrid perovskite crystals.

Halide vacancies and associated metallic lead (Pb°) observed at the surface and deep inside macroscopic organolead trihalide perovskite crystals is removed through a facile and noninvasive treatment. Indeed, Br2 vapor is shown to passivate Br-vacancies and associated Pb° in the bulk of macroscopic crystals. Controlling the exposure time can markedly improve the overall stoichiometry for moderate exposures or introduce excessive bromide for long exposures, resulting in p-doping of the crystals. In the low dose passivation regime, Hall effect measurements reveal a ca. 3-fold increase in carrier mobility to ca. 15 cm2V-1s-1, while the p-doping increases the electrical conductivity ca. 10000-fold, including a 50-fold increase in carrier mobility to ca. 150 cm2V-1s-1. The ease of diffusion of Br2 vapor into macroscopic crystals is ascribed to the porosity allowed in rapidly grown crystals through aggregative processes of the colloidal sol during growth of films and macroscopic crystals. This process is believed to form significant growth defects, including open voids, which may be remnants of the escaping solvent at the solidification front. These results suggest that due to the sol-gel-like nature of the growth process, macroscopic perovskite crystals reported in this study are far from perfect and point to possible pathways to improving the optoelectronic properties of these materials. Nevertheless, the ability of the vapor-phase approach to access and tune the bulk chemistry and properties of nominally macroscopic perovskite crystals provides interesting new opportunities to precisely manipulate and functionalize the bulk properties of hybrid perovskite crystals in a noninvasive manner.

Real-Space Mapping of Surface-Oxygen Defect States in Photovoltaic Materials Using Low-Voltage Scanning Ultrafast Electron Microscopy.

Ultrathin layers of native oxides on the surface of photovoltaic materials may act as very efficient carrier trapping/recombination centers, thus significantly affecting their interfacial photophysical properties. How ultrathin oxide layers affect the surface and interface carrier dynamics cannot be selectively accessed by conventional ultrafast transient spectroscopic methods due to the deep penetration depth (tens to thousands of nanometers) of the pump/probe laser pulses. Herein, scanning ultrafast electron microscopy (S-UEM) at a low voltage of 1 keV electrons was recently developed at KAUST to selectively map the ultrafast charge carrier dynamics of a few layers on the top surfaces of photovoltaic materials. Unlike high-voltage 30 keV experiments, at 1 keV, the depth of detected secondary electrons (SEs) underneath the surface is significantly reduced 5 times, thus making it possible to visualize the dynamics of charge carrier from the uppermost surface of photoactive layers. More specifically, this new approach has been employed to explore and decipher the tremendous impact of native oxide layers and oxygen defect states on charge carrier dynamics in space and time simultaneously at sub-nanometer levels on several photovoltaic material surfaces, including Si, GaAs, CdTe, and CdZnTe single crystals. Interestingly, the contrast in the SEs time-resolved difference images switched from a dark "energy-loss mechanism" to a bright "energy-gain mechanism" only by removing the layers of surface oxides. Moreover, the charge carrier recombination was estimated and found to be dramatically affected by the native oxide layers. The density functional theory (DFT) calculations demonstrate that the work function of oxygen-terminated Si surface also increases slightly upon optical excitation and makes for less SE intensity, providing another piece of evidence that the origin of the dark contrast observed on these material surfaces should be assigned to the surface oxide formation, mainly oxygen defect states in the band gap and/or work function increment. Our findings provide a new method and pave the way for evaluating the effect of surface morphology and defects, including but not limited to native oxide, on charge carrier dynamics, and interfacial properties of photovoltaic absorber layers.

Halogen Vacancies Enable Ligand-Assisted Self-Assembly of Perovskite Quantum Dots into Nanowires.

Interest has been growing in defects of halide perovskites in view of their intimate connection with key material optoelectronic properties. In perovskite quantum dots (PQDs), the influence of defects is even more apparent than in their bulk counterparts. By combining experiment and theory, we report herein a halide-vacancy-driven, ligand-directed self-assembly process of CsPbBr3 PQDs. With the assistance of oleic acid and didodecyldimethylammonium sulfide, surface-Br-vacancy-rich CsPbBr3 PQDs self-assemble into nanowires (NWs) that are 20-60 nm in width and several millimeters in length. The NWs exhibit a sharp photoluminescence profile (≈18 nm full-width at-half-maximum) that peaks at 525 nm. Our findings provide insight into the defect-correlated dynamics of PQDs and defect-assisted fabrication of perovskite materials and devices.

Pillar[5]arene-Stabilized Silver Nanoclusters: Extraordinary Stability and Luminescence Enhancement Induced by Host-Guest Interactions.

Herein, we report the synthesis of a new class of functional silver nanoclusters (AgNCs) capped with pillar[5]arene (P5)-based host ligands. These NCs are readily prepared through direct synthesis or ligand exchange synthesis and are stable at room temperature for over 4 months. The pillar[5]arene-stabilized NCs (Ag29 (LA-P5)12 (TPP)2 ) endorse reversible host-guest interactions with neutral alkylamines and cationic quaternary ammonium guests. This results in the formation of spherical assemblies with unparalleled changes in their optical properties including an astonishing circa 2000-fold luminescence enhancement. This is the highest luminescence enhancement ratio reported so far for such atomically precise NCs. Our synthetic protocol paves the way for the preparation of a new generation of metal nanoclusters protected by macrocyclic ligands with molecular recognition and selectivity toward specific guests.

Towards implementing hierarchical porous zeolitic imidazolate frameworks in dye-sensitized solar cells.

A one-pot method for encapsulation of dye, which can be applied for dye-sensitized solar cells (DSSCs), and synthesis of hierarchical porous zeolitic imidazolate frameworks (ZIF-8), is reported. The size of the encapsulated dye tunes the mesoporosity and surface area of ZIF-8. The mesopore size, Langmuir surface area and pore volume are 15 nm, 960-1500 m2 · g-1 and 0.36-0.61 cm3 · g-1, respectively. After encapsulation into ZIF-8, the dyes show longer emission lifetimes (greater than 4-8-fold) as compared to the corresponding non-encapsulated dyes, due to suppression of aggregation, and torsional motions.

MXenes for Plasmonic Photodetection.

MXenes have recently shown impressive optical and plasmonic properties associated with their ultrathin-atomic-layer structure. However, their potential use in photonic and plasmonic devices has been only marginally explored. Photodetectors made of five different MXenes are fabricated, among which molybdenum carbide MXene (Mo2 CTx ) exhibits the best performance. Mo2 CTx MXene thin films deposited on paper substrates exhibit broad photoresponse in the range of 400-800 nm with high responsivity (up to 9 A W-1 ), detectivity (≈5 × 1011 Jones), and reliable photoswitching characteristics at a wavelength of 660 nm. Spatially resolved electron energy-loss spectroscopy and ultrafast femtosecond transient absorption spectroscopy of the MXene nanosheets reveal that the photoresponse of Mo2 CTx is strongly dependent on its surface plasmon-assisted hot carriers. Additionally, Mo2 CTx thin-film devices are shown to be relatively stable under ambient conditions, continuous illumination and mechanical stresses, illustrating their durable photodetection operation in the visible spectral range. Micro-Raman spectroscopy conducted on bare Mo2 CTx film and on gold electrodes allowing for surface-enhanced Raman scattering demonstrates surface chemistry and a specific low-frequency band that is related to the vibrational modes of the single nanosheets. The specific ability to detect and excite individual surface plasmon modes provides a viable platform for various MXene-based optoelectronic applications.

Unprecedented Ultralow Detection Limit of Amines using a Thiadiazole-Functionalized Zr(IV)-Based Metal-Organic Framework.

A luminescent Zr(IV)-based metal-organic framework (MOF), with the underlying fcu topology, encompassing a π-conjugated organic ligand with a thiadiazole functionality, exhibits an unprecedented low detection limit of 66 nM for amines in aqueous solution. Markedly, this ultralow detection is driven by hydrogen-bonding interactions between the linker and the hosted amines. This observation is supported by density functional theory (DFT) calculations, which clearly corroborate the suppression of the twisting motion of thiadiazole core in the presence of amine, reducing significantly the nonradiative recombination pathways and subsequently enhancing the emission intensity. Credibly, nicotine regarded as a harmful chemical and bearing an amine pending group is also detected with high sensitivity, positioning this MOF as a potential sensor for practical environmental applications. This finding serves also as a benchmark to understand the sensing mechanism in MOFs.

Visualization of Charge Carrier Trapping in Silicon at the Atomic Surface Level Using Four-Dimensional Electron Imaging.

The ultrathin thickness (∼1-2 nm) of the native oxide layer on silicon surfaces, which acts as efficient trapping centers, precludes the possibility of studying its impact on the surface-charge carrier dynamics by conventional time-resolved laser spectroscopic techniques because of the large penetration depth of the pump and probe pulses. Here, we use four-dimensional scanning ultrafast electron microscopy (4D S-UEM) with unique surface sensitivity to directly visualize the charge carrier dynamics on Si(100) crystals before and after surface treatment (which removes the native oxide layer) in real space and time simultaneously. Our time-resolved snapshots of the top surface and Kelvin probe-force microscopy results demonstrate that the oxide layer can be formed within minutes after surface treatment, creating undesirable surface-trap states that destroy the population of photogenerated charge carriers on the surface and possibly at the device interface. This new surface observation provides critical photophysical insights into how a few atomic layers of oxide can dramatically influence charge carrier recombination dynamics in silicon solar cells.

Point Defects and Green Emission in Zero-Dimensional Perovskites.

Zero-dimensional (0D) perovskites have recently opened a new frontier in device engineering for light conversion technologies due to their unprecedented high photoluminescence quantum yield as solids. Although many experimental and theoretical efforts have been made to understand their optical behavior, the origin of their green emission is still opaque. Here, we develop a complete experimental and theoretical picture of point defects in Cs-Pb-Br perovskites and demonstrate that bromide vacancies (VBr) in prototype 0D perovskite Cs4PbBr6 have a low formation energy and a relevant defect level to contribute to the midgap radiative state. Moreover, the state-of-the-art characterizations including atomic-resolution electron imaging not only confirm the purity of the 0D phase of Br-deficient green-emissive Cs4PbBr6 nanocrystals (NCs) but also exclude the presence of CsPbBr3 NCs impurities. Our findings provide robust evidence for defect-induced green luminescence in 0D perovskite NCs, which helps extend the scope of the utility of these bulk 0D quantum materials in optoelectronic applications.

Light-Induced Interfacial Dynamics Dramatically Improve the Photocurrent in Dye-Sensitized Solar Cells: An Electrolyte Effect.

A significant increase in the photocurrent generation during light soaking for solar cells sensitized by the triphenylamine-based D-π-A organic dyes (PD2 and LEG1) and mediated by cobalt bipyridine redox complexes has been observed and investigated. The crucial role of the electrolyte has been identified in the performance improvement. Control experiments based on a pre-treatment strategy reveals TBP as the origin. The increase in the current and IPCE has been interpreted by the interfacial charge-transfer kinetics studies. A slow component in the injection kinetics was exposed for this system. This change explains the increase in the electron lifetime and collection efficiency. Photoelectron spectroscopic measurements show energy shifts at the dye/TiO2 interface, leading us to formulate a hypothesis with respect to an electrolyte-induced dye reorganization at the surface.