Time-resolved Infrared Spectroscopy Research Articles

Kinetics and Mechanism of Intramolecular Electron Transfer in Ru(II)-Re(I) Supramolecular CO2-Reduction Photocatalysts: Effects of Bridging Ligands.

The supramolecular photocatalysts in which a Ru(II) complex as a molecular redox photosensitizer unit and a Re(I) complex as a molecular catalyst unit are connected with a various alkyl or ether chain have attracted attention because they can efficiently photocatalyze CO2 reduction with high durability and high selectivity of CO formation, especially on various solid materials such as semiconductor electrodes and mesoporous organosilica. The intramolecular electron transfer from the one-electron reduced photosensitizer unit to the catalyst unit, which follows excitation of the photosensitizer unit and subsequent reductive quenching of the excited photosensitizer unit by a reductant, is one of the most important processes in the photocatalytic reduction of CO2. We succeeded in determining the rate constants of this intramolecular electron transfer process by using subnanosecond time-resolved IR spectroscopy. The logarithm of rate constants shows a linear relationship with the lengths of the bridging chain in the supramolecular photocatalysts with one bridging alkyl or ether chain. In conformity with the exponential decay of the wave function and the coupling element in the long-distance electron transfer, the apparent decay coefficient factor (β) in the supramolecular photocatalysts with one bridging chain was determined to be 0.74 Å-1. In the supramolecular photocatalyst with two ethylene chains connecting between the photosensitizer and catalyst units, on the other hand, the intramolecular electron transfer rate is much faster than that with only one ethylene chain. These results strongly indicate that the intramolecular electron transfer from the one-electron reduced species of the Ru photosensitizer unit to the Re catalyst unit proceeds by the through-bond mechanism.

Direct Spectroscopic Detection of Key Intermediates and the Turnover Process in Catalytic H2 Formation by a Biomimetic Diiron Catalyst

[FeFe(Cl2 -bdt)(CO)6 ] (1; Cl2 -bdt=3,6-dichlorobenzene-1,2-dithiolate), inspired by the active site of FeFe-hydrogenase, shows a chemically reversible 2 e- reduction at -1.20 V versus the ferrocene/ferrocenium couple. The rigid and aromatic bdt bridging ligand lowers the reduction potential and stabilizes the reduced forms, compared with analogous complexes with aliphatic dithiolates; thus allowing details of the catalytic process to be characterized. Herein, time-resolved IR spectroscopy is used to provide kinetic and structural information on key catalytic intermediates. This includes the doubly reduced, protonated complex 1H- , which has not been previously identified experimentally. In addition, the first direct spectroscopic observation of the turnover process for a molecular H2 evolving catalyst is reported, allowing for straightforward determination of the turnover frequency.

Capturing the Long-Lived Photogenerated Electrons in Au/TiO2 upon UV or Visible Irradiation by Time-Resolved Infrared Spectroscopy

Gold nanoparticle modifications for TiO2 (Au/TiO2) can extend the absorption wavelength from UV to visible (Vis) and enhance the photocatalytic performance, thus fueling increasing attention as an emerging photocatalysis strategy. To explore the plasmon-enhanced photocatalytic mechanism and directly unveil the intrinsic properties of Au/TiO2, the decay kinetics of photoelectrons upon UV (355 nm) or Vis (532 nm) excitation are monitored by means of nanosecond time-resolved infrared spectroscopy, which is a unique tool offering observations without interference of the holes. Under UV irradiation, the longer lifetime of photoelectrons observed in Au/TiO2 compared to that in bare TiO2 provides unambiguous evidence for the enhanced charge separation by AuNPs. Under Vis irradiation, the long-lived (hundreds of microseconds) electrons produced by injection from AuNPs into TiO2 upon plasmon excitation are here detected for the first time. Moreover, the effects of TiO2 phase composition and the amount of AuNPs loa...

Generation of Microsecond Charge-Separated Excited States in Rhenium(I) Diimine Complexes: Driving Force Is the Dominant Factor in Controlling Lifetime.

A transition-metal-based donor-(linker)-acceptor system can produce long-lived charge transfer excited states using visible excitation wavelengths. The ground- and excited-state photophysical properties of a series of [ReCl(CO)3(dppz-(linker)-TPA)] complexes, with varying donor and acceptor energies, have been systematically studied using spectroscopic techniques (both vibrational and electronic) supported by computational chemistry. The long-lived excited state is 3ILCT in nature for all complexes studied, characterized through transient absorption and emission, transient resonance Raman (TR2), and time-resolved infrared (TRIR) spectroscopy and TDDFT calculations. Modulation of the donor and acceptor energies results in changes of the 3ILCT lifetime by 1 order of magnitude, ranging from 6.1(±1) μs when a diphenylamine donor is used to 0.6(±0.2) μs when a triazole linker and triphenylamine donor is used. The excited-state lifetime may be rationalized by consideration of the driving force within the framework of Marcus theory and appears insensitive to the nature of the linker.

Monitoring the Formation and Reactivity of Organometallic Alkane and Fluoroalkane Complexes with Silanes and Xe Using Time-Resolved X-ray Absorption Fine Structure Spectroscopy.

Complexes with weakly coordinating ligands are often formed in chemical reactions and can play key roles in determining the reactivity, particularly in catalytic reactions. Using time-resolved X-ray absorption fine structure (XAFS) spectroscopy in combination with time-resolved IR (TRIR) spectroscopy and tungsten hexacarbonyl, W(CO)6, we are able to structurally characterize the formation of an organometallic alkane complex, determine the W-C distances, and monitor the reactivity with silane to form an organometallic silane complex. Experiments in perfluorosolvents doped with xenon afford initially the corresponding solvated complex, which is sufficiently reactive in the presence of Xe that we can then observe the coordination of Xe to the metal center, providing a unique insight into the metal-xenon bonding. These results offer a step toward elucidating the structure, bonding, and chemical reactivity of transient species by X-ray absorption spectroscopy, which has sensitivity to small structural changes. The XAFS results indicate that the bond lengths of metal-alkane (W-H-C) bond in W(CO)5(heptane) as 3.07 (±0.06) Å, which is longer than the calculated W-C (2.86 Å) for binding of the primary C-H, but shorter than the calculated W-C (3.12 Å) for the secondary C-H. A statistical average of the calculated W-C alkane bond lengths is 3.02 Å, and comparison of this value indicates that the value derived from the XAFS measurements is averaged over coordination of all C-H bonds consistent with alkane chain walking. Photolysis of W(CO)6 in the presence of HSiBu3 allows the conversion of W(CO)5(heptane) to W(CO)5(HSiBu3) with an estimated W-Si distance of 3.20 (±0.03) Å. Time-resolved TRIR and XAFS experiments following photolysis of W(CO)6 in perfluoromethylcyclohexane (PFMCH) allows the characterization of W(CO)5(PFMCH) with a W-F distance of 2.65 (±0.06) Å, and doping PFMCH with Xe allows the characterization of W(CO)5Xe with a W-Xe bond length of 3.10 (±0.02) Å.

Monitoring Base-Specific Dynamics during Melting of DNA-Ligand Complexes Using Temperature-Jump Time-Resolved Infrared Spectroscopy.

Ultrafast time-resolved infrared spectroscopy employing nanosecond temperature-jump initiation has been used to study the melting of double-stranded (ds)DNA oligomers in the presence and absence of minor groove-binding ligand Hoechst 33258. Ligand binding to ds(5'-GCAAATTTCC-3'), which binds Hoechst 33258 in the central A-tract region with nanomolar affinity, causes a dramatic increase in the timescales for strand melting from 30 to ∼250 μs. Ligand binding also suppresses premelting disruption of the dsDNA structure, which takes place on 100 ns timescales and includes end-fraying. In contrast, ligand binding to the ds(5'-GCATATATCC-3') sequence, which exhibits an order of magnitude lower affinity for Hoechst 33258 than the A-tract motif, leads to an increase by only a factor of 5 in melting timescales and reduced suppression of premelting sequence perturbation and end-fraying. These results demonstrate a dynamic impact of the minor groove ligand on the dsDNA structure that correlates with binding strength and thermodynamic stabilization of the duplex. Moreover, the ability of the ligand to influence base pairs distant from the binding site has potential implications for allosteric communication mechanisms in dsDNA.

(Invited) Dye-Sensitized Metal Oxides for Artificial Photosynthesis

Efficient dye-sensitized photocathodes offer new opportunities for converting sunlight into storable energy cheaply and sustainably. We are developing photocathodes based on dye-sensitized metal oxides for light-driven reduction of carbon dioxide or water to higher energy products (solar fuels) using the lessons we have learnt from solar cells. Despite the infancy and complexity of this research area, we have brought about a number of exciting developments which have improved our understanding of the system. We are tackling the main limitations to photocurrent, by improving the quality of the mesoporous electrodes and engineering new photocatalysts specifically for the p-type system, to increase the quantum efficiency of the device. The electron-transfer dynamics are key to the performance and a major challenge is slowing down charge recombination between the photoreduced dye and the oxidised NiO so that chemistry can take place. Highlights from recent work examining charge-transfer at the interface between metal oxides and new supramolecular photocatalysts using transient absorption spectroscopy and time-resolved infrared spectroscopy will be presented alongside the photoelectrochemical characteristics of the devices. Dye-sensitized photocathodes for H2 evolution, E. A. Gibson, Chemical Society Reviews, 2017, 46, 6194 – 6209. Photoelectrocatalytic H2 Evolution from Integrated Photocatalysts Adsorbed on NiO, N. Põldme, L. O’Reilly, I. Fletcher, I. Sazanovich, M. Towrie, C. Long, J. G. Vos, M. T. Pryce, E. A. Gibson Chem. Sci., 2019,10, 99-112. Rapid photoinduced charge injection into covalent polyoxometalate-bodipy conjugates. F. A. Black, A. Jacquart, G. Toupalas, S. Alves, A. Proust, I. P. Clark, E. A. Gibson*, G. Izzet. Chem. Sci., 2018, 9, 5578-5584

Efficient Charge Carrier Separation in l-Alanine Acids Derived N-TiO2 Nanospheres: The Role of Oxygen Vacancies in Tetrahedral Ti4+ Sites.

N-doped TiO2 with oxygen vacancies exhibits many advantages for photocatalysis, such as enhanced visible light absorbency, inhibition of the photogenerated charge carrier recombination, etc. However, preparation of N-doped TiO2 with oxygen vacancies under mild conditions is still a challenge. Herein, N-doped TiO2 nanospheres with tetrahedral Ti4+ sites were synthesized by using dodecylamine as template and assisted by l-alanine acids. The obtained samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV–Vis diffuse reflectance spectra (UV–Vis DRS). It was found that the dodecylamine as a neutral surfactant controlled the structure of TiO2 spherical, while l-alanine acids provided a nitrogen source. The existence of tetrahedral Ti4+ sites in N-doped TiO2 was also confirmed. The N-doped TiO2 sample with tetrahedral Ti4+ sites exhibited significantly improved photocatalytic performance for degradation of methylene blue solution under UV light or visible light irradiation. A combined time-resolved infrared (IR) spectroscopy study reveals that the enhanced photocatalytic performance could be attributed to a large amount of photogenerated charge carriers and efficient charge separation. It is demonstrated that the shallow donor state produced by oxygen vacancies of tetrahedral Ti4+ sites can effectively promote separation of charge carriers besides capturing electrons.

Disentangling Time Scales of Vibrational Cooling, Solvation, and Hydrogen Bond Reorganization Dynamics Using Ultrafast Transient Infrared Spectroscopy of Formylperylene.

Unraveling dynamics of solvation and hydrogen bond (H-bond) reorganization between a solute and solvent is crucial to understand the importance of specific and nonspecific interactions in a solution-phase chemical reaction. Ultrafast time-resolved infrared (TRIR) spectroscopy provides direct opportunity to monitor site-specific intermolecular dynamics on a real-time scale by probing vibrational marker bands in the excited state of a solute. Herein, we report the real-time dynamics of vibrational cooling, solvation, and hydrogen bond reorganization of formylperylene (FPe) through TRIR spectroscopy of carbonyl (C═O) stretching mode in nonpolar, polar aprotic, and polar protic solvents. High sensitivity of the C═O stretch frequency (υ̅C═O) to photoinduced intramolecular charge transfer processes induced by specific and nonspecific solvent interactions led us to monitor the dynamics of dipolar solvation, site-specific H-bond formation, and reorganization processes by the TRIR method. In nonpolar cyclohexane, the υ̅C═O stretch band appears at 1610 cm-1 and exhibits negligible spectral shift over several tens of picoseconds. In acetonitrile, the υ̅C═O peak shifts to 1594 cm-1 and exhibits a further temporal red shift of about 5 cm-1 with a characteristic solvation time scale of acetonitrile (τ ∼ 0.5 ps). In methanol, υ̅C═O exhibits two bands corresponding to free and H-bonded FPe in early time scale. The free FPe population converts to the hydrogen-bonded population with a lifetime of about 10 ps. Vibrational cooling (τvc ∼ 12-20 ps) in the excited electronic state of FPe could independently be monitored from the temporal dynamics of the ring vibration mode, which is less sensitive to solvation and hydrogen bonding. The present study provides insight into the specific and nonspecific solvation-controlled charge transfer dynamics in aprotic and protic solvents using FPe as a probe.

(Invited) New Mixed-Anion Photocatalysts for Water Splitting and CO2 Fixation

Water splitting and CO2 fixation using semiconductor photocatalysts are important reactions from the viewpoint of solar-to-fuel energy conversion toward artificial photosynthesis. Mixed-anion compounds containing more than one anionic species in a single-phase have attracted attention as visible-light-driven photocatalysts, since as compared to oxygen 2p orbital, p orbitals of less electronegative anion can form a valence band that possesses more negative potential. In this talk, recent progress on the development of new mixed-anion photocatalysts that are applicable to water splitting and CO2 fixation will be given. We developed Ta and N-codoped rutile TiO2 for visible-light-driven water oxidation. TiO2:Ta,N powders modified with a RuO2 cocatalyst were active under visible light up to 540 nm for water oxidation to produce O2 in the presence of reversible electron acceptors (IO3 – or Fe3+), while TiO2:N exhibited negligible activity. Results of time-resolved infrared absorption spectroscopy revealed that the codoping Ta with N into TiO2 prolonged the lifetime of photogenerated free electrons, leading to high photocatalytic activity. Overall water splitting into H2 and O2 was achieved using TiO2:Ta,N, in combination with a H2-evolution photocatalyst of SrTiO3:Rh and an Fe3+/Fe2+ or IO3 –/I– redox couple even under simulated sunlight (AM1.5G). A similar result was obtained with rutile TiO2 codoped with N and F. TiO2:Ta,N also served as a very stable photoanode to oxidize water under visible light, and could be coupled to not only a H2 evolution cathode but also a molecular photocathode for CO2 reduction. A photoelectrochemical cell constructed with RuO2/TiO2:Ta,N photoanode and Ru(II)–Re(I) supramolecular photocathode was capable of reducing CO2 into CO using water as the electron source upon visible light, with stoichiometric production of CO and O2. Another interesting example of mixed-anion photocatalyst is an oxyfluoride pyrochlore Pb2Ti2O5.4F1.2. It had been believed that oxyfluorides are unsuitable as visible-light-responsive photocatalysts because of the highest electronegativity of fluorine. Surprisingly, Pb2Ti2O5.4F1.2 had an unprecedented small band gap of ca. 2.4 eV, and worked as a stable photocatalyst for visible-light H2 evolution and CO2 reduction when modified with suitable promoters. Density functional theory calculations indicated that the unprecedented visible-light-response of Pb2Ti2O5.4F1.2 originates from strong interaction between Pb-6s and O-2p orbitals, which is enabled by a short Pb–O bond in the pyrochlore lattice due to the fluorine substitution.

Self-calibrating time-resolved near infrared spectroscopy

Time-resolved near infrared spectroscopy is considered to be a gold standard technique when measuring absolute values of tissue optical properties, as it provides separable and independent information about both tissue absorption and scattering. However, time-resolved instruments require an accurate characterization by measuring the instrument response function in order to decouple the contribution of the instrument itself from the measurement. In this work, a new approach to the methodology of analysing time-resolved data is presented where the influence of instrument response function is eliminated from the data and a self-calibrating analysis is proposed. The proposed methodology requires an instrument to provide at least two wavelengths and allows spectral parameters recovery (optical properties or constituents concentrations and reduced scatter amplitude and power). Phantom and in-vivo data from two different time-resolved systems are used to validate the accuracy of the proposed self-calibrating approach, demonstrating that parameters recovery compared to the conventional curve fitting approach is within 10% and benefits from introducing a spectral constraint to the reconstruction problem. It is shown that a multi-wavelength time-resolved data can be used for parameters recovery directly without prior calibration (instrument response function measurement).

Tracking Pore Hydration in Channelrhodopsin by Site-Directed Infrared-Active Azido Probes.

In recent years, gating and transient ion-pathway formation in the light-gated channelrhodopsins (ChRs) have been intensively studied. Despite these efforts, a profound understanding of the mechanistic details is still lacking. To track structural changes concomitant with the formation and subsequent collapse of the ion-conducting pore, we site-specifically introduced the artificial polarity-sensing probe p-azido-l-phenylalanine (azF) into several ChRs by amber stop codon suppression. The frequently used optogenetic actuator ReaChR (red-activatable ChR) exhibited the best expression properties of the wild type and the azF mutants. By exploiting the unique infrared spectral absorption of azF [νas(N3) ∼ 2100 cm-1] and its sensitivity to polarity changes, we monitored hydration changes at various sites of the pore region and the inner gate by stationary and time-resolved infrared spectroscopy. Our data imply that channel closure coincides with a dehydration event occurring between the interface of the central and the inner gate. In contrast, the extracellular ion pathway seems to be hydrated in the open and closed states to similar extents. Mutagenesis of sites in the inner gate suggests that it acts as an intracellular entry funnel, whose architecture and composition modulate water influx and efflux within the channel pore. Our results highlight the potential of genetic code expansion technology combined with biophysical methods to investigate channel gating, particularly hydration dynamics at specific sites, with a so far unprecedented spatial resolution.

Structural origins of the electronic properties of materials via time-resolved infrared spectroscopy

Time-resolved mid-infrared spectroscopy provides new opportunities to probe the structural origins of electronic and transport states in optoelectronic materials.

Time-resolved IR spectroscopy reveals mechanistic details of ion transport in the sodium pump Krokinobacter eikastus rhodopsin 2.

We report a comparative study on the structural dynamics of the light-driven sodium pump Krokinobacter eikastus rhodopsin 2 wild type under sodium and proton pumping conditions by means of time-resolved IR spectroscopy. The kinetics of KR2 under sodium pumping conditions exhibits a sequential character, whereas the kinetics of KR2 under proton pumping conditions involves several equilibrium states. The sodium translocation itself is characterized by major conformational changes of the protein backbone, such as distortions of the α-helices and probably of the ECL1 domain, indicated by distinct marker bands in the amide I region. Carbonyl stretch modes of specific amino acid residues helped to elucidate structural changes in the retinal Schiff base moiety, including the protonation and deprotonation of D116, which is crucial for a deeper understanding of the mechanistic features in the photocycle of KR2.

Understanding Elementary Steps of Transport of Xylene Mixtures in ZSM-5 Zeolites

The transport of p-xylene in purely siliceous MFI was investigated in the presence of coadsorbed m-xylene by combining fast time-resolved IR spectroscopy and frequency response methods. p-Xylene transport rates are dominated by diffusion in the straight channels of MFI, which is 8 times faster than transport in the sinusoidal channels. m-Xylene adsorbed on the outer surface lowers the sorption rate of p-xylene significantly by blocking pore entrances, whereas m-xylene adsorbed in the MFI pores hardly influences the p-xylene transport rates. If the pore entrance is the rate-determining step of the transport process, as for the MFI samples investigated, m-xylene sorption on the outer surface selectively impedes faster transport through the straight pore openings

A novel setup for time-resolved IR spectroscopy on Cytochrome c Oxidase

A novel setup for time-resolved IR spectroscopy on Cytochrome c Oxidase

Photophysical and electrochemical properties of [Re(CO)3Cl(NN)] (NN = dppp3, dppp2, dppp2Br) complexes functionalised with pendant pyridyl ligands

We report the synthesis, electrochemical, and photophysical properties of a series of rhenium complexes, [Re(CO)3Cl(NN)] (NN = dppp2, dppp3, and dppp2Br; dppp2 = pyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline, dppp3 = pyrido[3′,4′:5,6]pyrazino[2,3-f][1,10]phenanthroline, dppp2Br = 8-bromopyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline), which have potential for use as CO2 photoreduction catalysts. The complexes are related to [Re(CO)3Cl(dppz)] (dppz = dipyrido[3,2-a:2′,3′-c]phenazine) but have an additional nitrogen heteroatom in the distal phenazine (phz) aromatic ring of the dppz ligand which is known to promote potential photoinduced CO2 binding and reduction in related complexes. We use Fourier transform infrared (FTIR), UV/Visible, electron paramagnetic resonance (EPR) and time-resolved infrared (TRIR) spectroscopies to investigate how the location of the additional nitrogen atom, and how the nature of the substituents affects the photophysical properties. In addition, the one electron reduced catalysts are generated following bulk electrochemical reduction and characterised in CH2Cl2. TRIR experiments in d6-DMSO, CH3CN, CH2Cl2, THF and toluene reveal that excitation generates a 3MLCT(phz) (phz = phenazine) excited state in all compounds. In CH3CN and d6-DMSO (not for [Re(CO)3Cl(dppp2)]), we observe the concomitant formation of an 3IL ππ* (IL = intra ligand) excited state. For [Re(CO)3Cl(dppp2)] and [Re(CO)3Cl(dppp3)] in toluene, a mixture of 3MLCT(phen) (phen = phenanthroline) and 3MLCT(phz) states appear to form together, and decay at the same rate. Inclusion of an nitrogen atom in the phz moiety of the dppz ligand lowers the ‘phz’ localised lowest unoccupied molecular orbital (LUMO) energy potentially favouring population of the 3MLCT(phz) state. This effect is more pronounced for [Re(CO)3Cl(dppp3)] with a more positive reduction potential (E½ = −1.16 vs Fc+/Fc in CH2Cl2) compared to [Re(CO)3Cl(dppp2)] (E½ = −1.20 V vs Fc+/Fc in CH2Cl2). For [Re(CO)3Cl(dppp2Br)], lowering of the LUMO energy results in an even more positive potential (E½ = −1.10 vs Fc+/Fc in CH2Cl2) and this can be seen to affect the photophysics. We find the excited state lifetime for each complex increases with decreasing dielectric constant, where their lifetime in toluene is greater than 100 times longer than that observed in d6-DMSO.

Non-Singlet Oxygen Kinetic Solvent Isotope Effects in Aquatic Photochemistry.

The kinetic solvent isotope effect (KSIE) is typically utilized in environmental photochemistry to elucidate whether a compound is susceptible to photooxidation by singlet oxygen (1O2), due to its known difference in lifetime in water (H2O) versus heavy water (D2O). Here, the overall indirect photodegradation rates of diarylamines in the presence of dissolved organic matter (DOM) were enhanced in D2O to a greater extent than expected based on their reactivity with 1O2. For each diarylamine, the relative contribution of reaction with 1O2 to the observed KSIE was determined from high resolution data of 1O2 lifetimes by time-resolved infrared luminescence spectroscopy. The additional enhancement in D2O beyond reaction with 1O2 contributed significantly to the observed KSIE for diarylamines (8-65%) and diclofenac (100%). The enhancement was ascribed to slower reduction of transient radical species of the diarylamines due to H/D exchange at DOM's phenolic antioxidant moieties. A slower second-order reaction rate constant with a model antioxidant was verified for mefenamic acid radicals using transient absorption spectroscopy. Changes in lifetime and reactivity with triplet sensitizers were not responsible for the additional KSIE. Other pollutants with quenchable radical intermediates may also be susceptible to such an additional KSIE, which has to be considered when using the KSIE as a diagnostic tool.

Mechanism of Methanol Inhibition of Photosynthetic Water Oxidation As Studied by Fourier Transform Infrared Difference and Time-Resolved Infrared Spectroscopies.

Photosynthetic water oxidation is performed at the Mn4CaO5 cluster in photosystem II. In this study, we investigated the effect of methanol, an analogue of water, on the water oxidation reaction and its interaction site using Fourier transform infrared (FTIR) difference and time-resolved infrared (TRIR) spectroscopies. Flash-induced FTIR difference measurement of the S-state cycle showed that methanol decreases mainly the efficiency of the S3 → S0 transition. TRIR measurement further showed that methanol slowed the rates of the S2 → S3 and S3 → S0 transitions. FTIR difference spectra upon the S1 → S2 transition exhibited prominent methanol-induced changes in the amide I and II bands of the main chains, whereas little change was observed in the bands of carboxylate groups, histidine side chains, and a water network in the vicinity of the Mn4CaO5 cluster. Similar tendencies were also observed with ethanol and 2-propanol. The C-O stretching vibration of methanol was further identified in the S2-minus-S1 spectrum using 18O-labeled methanol. These results indicate that methanol and small alcohols are bound near the Mn4CaO5 cluster but with no direct interaction. They probably replace a water molecule in a water channel around the Mn4CaO5 cluster, possibly interacting with a main chain amide. It is thus suggested that this replacement of water with methanol or a small alcohol inhibits water/proton transfer during the S2 → S3 and S3 → S0 transitions, which in turn provides experimental support for the view that these two transitions involve the water uptake and proton release processes.

Near infrared light induced plasmonic hot hole transfer at a nano-heterointerface

Localized surface plasmon resonance (LSPR)-induced hot-carrier transfer is a key mechanism for achieving artificial photosynthesis using the whole solar spectrum, even including the infrared (IR) region. In contrast to the explosive development of photocatalysts based on the plasmon-induced hot electron transfer, the hole transfer system is still quite immature regardless of its importance, because the mechanism of plasmon-induced hole transfer has remained unclear. Herein, we elucidate LSPR-induced hot hole transfer in CdS/CuS heterostructured nanocrystals (HNCs) using time-resolved IR (TR-IR) spectroscopy. TR-IR spectroscopy enables the direct observation of carrier in a LSPR-excited CdS/CuS HNC. The spectroscopic results provide insight into the novel hole transfer mechanism, named plasmon-induced transit carrier transfer (PITCT), with high quantum yields (19%) and long-lived charge separations (9.2 μs). As an ultrafast charge recombination is a major drawback of all plasmonic energy conversion systems, we anticipate that PITCT will break the limit of conventional plasmon-induced energy conversion.