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Which radical/anion pair will be formed upon one-electron reduction (mesolysis of radical anion)?

In this study, we synthesized radioexcitable luminescent polymer dots (P-dots) doped with heteroleptic tris-cyclometalated iridium complexes that emit red, green, and blue light.

New NO-generating nanoparticles employing an intermolecular photoredox reaction successfully released NO upon blue light irradiation in vitro.

We demonstrate that polymer dots doped with thermally activated delayed fluorescence (TADF) molecules clearly exhibit blue radio-luminescence upon hard X-ray and electron beam irradiation, which is a new design for nano-sized scintillators.

Fluorescence imaging uses changes in the fluorescence intensity and emission wavelength to analyze multiple targets simultaneously. To increase the number of targets that can be identified simultaneously, fluorescence blinking can be used as an additional parameter. To understand and eventually control blinking, we used DNA as a platform to elucidate the processes of electron transfer (ET) leading to blinking, down to the rate constants. With a fixed ET distance, various blinking patterns were observed depending on the DNA sequence between the donor and acceptor units of the DNA platform. The blinking pattern was successfully described with a combination of ET rate constants. Therefore, molecules with various blinking patterns can be developed by tuning ET. It is expected that the number of targets that can be analyzed simultaneously will increase by the power of the number of blinking patterns.

Rutile TiO2 nanorods with lengths greater than 600 nm and aspect ratios greater than ca. 16 were synthesized through a one-pot hydrothermal method using lactic acid (LA) as a structure-directing agent. Under the hydrothermal treatment at 200 °C, the LA concentration higher than 1.6 mol dm–3 and the hydrothermal time of 72 h were needed to obtain 100% rutile nanorods. The length and the width of the nanorods increased with the increasing LA concentration. The photocatalytic activity of the synthesized nanorods was evaluated for the oxygen evolution in aqueous AgNO3 solutions under ultraviolet irradiation. Calcination of the synthesized nanorods at 400 °C was required to decompose residual organic compounds on the surface and improve the oxygen evolution. The highest oxygen evolution rate was obtained with the nanorods after being calcined at 800 °C. It is worth noting that the nanorods retained their shape (aspect ratio of 8.8) at 800 °C. Selected area electron diffraction patterns indicated that the side or the end surface of the nanorods was attributable to the {110} or {111} facet, respectively. Deposition of Pt or PbO2 on the nanorods revealed that the {110} or {111} facet acted as reductive or oxidative sites. For comparison, near-spherical TiO2 nanoparticles were synthesized by a sol–gel method. Furthermore, using glycolic acid as the structure-directing agent, we synthesized small rutile TiO2 nanorods (aspect ratio of 9) and changed the shape to near-spherical (aspect ratio of 1.3) by calcining at 800 °C. Time-resolved diffuse reflectance spectra were measured to determine the lifetime of the photogenerated electrons. The photocatalytic activity of the nanorods was much lower than that of the near-spherical TiO2 nanoparticles. However, the nanorods synthesized with LA are useful as catalyst support or platforms for various applications because of their unique morphology and high heat resistance.

Pristine and Bi-doped lanthanum titanium oxide (La2Ti2O7) nanosheets have been synthesized as photocatalysts for overall solar water splitting. The surface hole trap is a critical factor that limits the photocatalytic activity of pristine La2Ti2O7. Deposition of cobalt phosphate (Co-Pi) and platinum (Pt) nanoparticles on La2Ti2O7 cannot remove the surface traps although they are essential for enabling the oxygen and hydrogen evolution reactions. It is interesting that doping bismuth (Bi) into La2Ti2O7 nanosheets has eliminated the surface traps due to surface enrichment of Bi. The Co-Pi/Bi-La2Ti2O7/Pt nanosheets exhibit increasing photocatalytic activity toward overall water splitting with increasing the Bi-dopant level up to 5 at.%. Further increasing the Bi-dopant level leads to the formation of localized states above the valence band, leading to the lifetime reduction of photogenerated charge-carriers, and jeopardizing the photocatalytic activity. This work proposes an effective strategy to address the surface trapping and surface catalysis issues in the nanostructured metal oxide photocatalysts.

To explore the dynamics of biomolecules, tracing the kinetics of photo-induced chemical reactions via the triplet excited state (T1 ) of probe molecules offers a timescale that is about 106 times wider than via the singlet excited state (S1 ). Using cyclooctatetraene (COT) as a triplet energy acceptor and at the same time as a photostabilizer, the triplet-triplet energy transfer (TTET) kinetics governed by oligonucleotide (oligo) dynamics were studied at the single-molecule level by measuring fluorescence blinking. TTET kinetics measurement allowed us to access the length- and sequence-dependent dynamics of oligos and realize the single-molecule detection of a model microRNA biomarker. In sharp contrast to the singlet-singlet Forster resonance energy transfer (FRET) that occurs in the 1-10 nm range, TTET requires a Van der Waals contact. The present method is thus a complementary method to FRET and provides direct information on biomolecular dynamics on the μs to ms timescale.

Recent advances in fluorescence microscopy allow us to track chemical reactions at the single-molecule level. Single-molecule measurements make it possible to minimize the amount of sample needed for analysis and diagnosis. Signal amplification is often applied to ultralow-level biomarker detection. Polymerase chain reaction (PCR) is used to detect DNA/RNA, and enzyme-linked immunosorbent assay (ELISA) can sensitively probe antigen-antibody interactions. While these techniques are brilliant and will continue to be used in the future, single-molecule-level measurements would allow us to reduce the time and cost needed to amplify signals.The kinetics of chemical reactions have been studied mainly using ensemble-averaged methods. However, they can hardly distinguish time-dependent fluctuations and static heterogeneity of the kinetics. The information hidden in ensemble-averaged measurements would be extractable from a single-molecule experiment. Thus, single-molecule measurement would provide unique opportunities to investigate unrevealed phenomena and to elucidate the questions in chemistry, physics, and life sciences. Redox reaction, which is triggered by electron transfer, is among the most fundamental and ubiquitous chemical reactions. The redox reaction of a fluorescent molecule results in the formation of radical ions, which are normally nonemissive. In single-molecule-level measurements, the redox reaction causes the fluctuation of fluorescence signals between the bright ON-state and the dark OFF-state, in a phenomenon called blinking. The duration of the OFF-state (τOFF) corresponds to the lifetime of the radical ion state, and its reaction kinetics can be measured as 1/τOFF. Thus, the kinetics of redox reactions of fluorescent molecules can be accessed at the single-molecule level by monitoring fluorescence blinking. One of the key aspects of single-molecule analysis based on blinking is its robustness. A blinking signal with a certain regular pattern enables single fluorescent molecules to be distinguished and resolved from the random background signal.In this Account, we summarize the recent studies on the single-molecule measurement of redox reaction kinetics, with a focus on our group's recent progress. We first introduce the control of redox blinking to increase the photostability of fluorescent molecules. We then demonstrate the control of redox blinking, which allows us to detect target DNA by monitoring the function of a molecular beacon-type probe, and we investigate antigen-antibody interactions at the single-molecule level. By tracing the time-dependent changes in blinking patterns, redox blinking is shown to be adaptable to tracking the structural switching dynamics of RNA, the preQ1 riboswitch. This Account ends with a discussion of our ongoing work on the control of fluorescent blinking. We also discuss the development of devices that allow single-molecule-level analysis in a high-throughput fashion.

We report the aggregation-induced photosensitizing activity of a cyanine dye in water and the mechanism. In addition, using the supramolecular assembly, visible-light-driven photooxidation of hydrophobic aromatic compounds in water was successfully performed.

Photocatalysis holds great potential in alleviating the growing energy crisis and environmental issues. Defect engineering has been demonstrated as an effective method to modulate the electronic structure of semiconductor photocatalysts for enhanced visible light absorption. However, the effect of defects on photocatalytic activity is still under debate because of the elusive charge transfer process mediated by defects. In this feature article, we summarize our recent progress in unraveling the defect-mediated electron transfer of the widely studied TiO2 and polymeric carbon nitride photocatalysts by combining ultrafast time-resolved spectroscopy and theoretical simulations. We find that the photogenerated electron transfer is greatly dependent on the type and concentration of defects. The location and occupation of defect states, and the dispersion degree of the energy band should be carefully tuned to maximize the advantages of defects for photocatalytic reactions.

Porphyrin covalent organic nanodisks were synthesized by exfoliating covalent organic frameworks in acidic aqueous solutions at pH 4. Showed remarkable bactericidal activity against E. coli owing to enhanced generation of singlet oxygen upon visible light irradiation.

Photosensitizers (PSs) are critical substances with considerable potential for use in non-invasive photomedicine. Type I PSs, which generate reactive radical species by electron transfer from the excited state induced via photoirradiation, attracted much attention because of their suitability for photodynamic therapy (PDT) irrespective of the oxygen concentration. However, most organic PSs are type II, which activates only oxygen, generating singlet oxygen (

Hard X-ray excited optical luminescence is a unique property of materials, which makes them promising for biological imaging applications. However, the preparation of biocompatible contrast agents for hard X-ray excited optical luminescence remains a considerable challenge that has, to date, not been overcome. In this study, we investigated the luminescence properties of protein-directed Au∼20 clusters upon hard X-ray irradiation, both in solution and when embedded in films.

Designing photocatalysts with appropriate intrinsic active sites for the hydrogen evolution reaction (HER) and efficient charge-carrier separation is critical to get rid of the dependence on co-catalysts. Herein, we for the first time trigger the catalytic activity of inert basal plane S atoms in two-dimensional hexagonal ZnIn2S4 (ZIS) via Ni atom doping (Ni-ZIS). Density functional theory calculations (DFT) and X-ray absorption fine structure (XAFS) investigations reveal that Ni atoms preferably replace Zn atoms in ZIS. And introducing Ni atoms would form new hybridized states near the Fermi level and modulate the electronic properties of their neighboring S atoms, leading to optimized hydrogen adsorption free energy and enhanced HER kinetics. Additionally, fs-transient absorption spectroscopy measurements illustrate a prolonged recovery lifetime of photoexcited electrons in Ni-ZIS. Consequently, Ni-ZIS exhibits an improved photocatalytic activity with a hydrogen evolution rate of 4220 μmol g−1 h−1 under visible light irradiation (λ > 420 nm) without any co-catalysts, roughly 3.2 times higher than that of ZIS. The apparent quantum efficiency at 380 and 420 nm could reach as high as 19.7% and 17.1%, respectively. This single atom modulation strategy presents a facile and promising pathway to enhance the photocatalytic activity of ZIS for the HER without co-catalysts.

A B12 complex–BODIPY dyad was synthesized by peripheral modification of cobalamin derivatives. The photophysical properties of the dyad were investigated by UV-vis, PL, and transient absorption spectroscopy. A visible light-driven dechlorination reaction of a trichlorinated organic compound, DDT, was reported. The dyad showed efficient catalysis for dechlorination under N2 with turnover numbers of over 220 for the reaction. One-pot syntheses of an ester and amide from DDT and benzotrichloride were also achieved using the dyad under air.

Reductive dehalogenation of aryl halides, bromobenzonitrile and iodobenzonitrile by the photo-excited B12 complex with the labile Co(I) oxidation state under anaerobic conditions was reported for t...

For photocatalysis, clarifications of charge carrier migration route and kinetics on individual particles by photoluminescence (PL) are of great importance because they play significant roles on unveiling the precise information of structure-activity relationships and closely relate to the photocatalytic activities of those semiconductors on targeted functions. Here, photodeposition process of NiS nanoparticles on single TiO2 mesocrystal (TMC) as co-catalyst is in situ monitored by PL images and spectra using a confocal single-particle PL microscopy, which provides straightforward results on understanding the photoexcited electrons transfer in both individual TMC and TMC/NiS nanoparticles. Through the changes in PL intensity and decay lifetime, preferential trapping site for NiS nanoparticles on TMC is identified and efficient electron interfacial migration from TMC to NiS nanoparticles is demonstrated, which lead to an almost 71 folds enhancement on the photocatalytic H2 evolution under 365-nm photoirradiation compared to pure TMC particles.

The exposed active sites of semiconductor catalysts are essential to the photocatalytic energy conversion efficiency. However, it is difficult to directly observe such active sites and understand the photogenerated electron/hole pairs' dynamics on a single catalyst particle. Here, we applied a quasi-total internal reflection fluorescence microscopy and laser-scanning confocal microscopy to identify the photocatalytic active sites at a single-molecule level and visualized the photogenerated hole-electron pair dynamics on a single TiO2 particle, the most widely used photocatalyst. The experimental results and density functional theory calculations reveal that holes and electrons tend to reach and react at the same surface sites, i.e., crystal edge/corner, within a single anatase TiO2 particle owing to the highly exposed (001) and (101) facets. The observation provides solid proof for the existence of the surface junction "edge or corner" on single TiO2 particles. These findings also offer insights into the nature of the photocatalytic active sites and imply an activity-based strategy for rationally engineering catalysts for improved photocatalysis, which can be also applied for other catalytic materials.

TiO2 nanorods have been widely investigated for various applications as catalyst support, photoanode, bioanalytical platform, and photocatalyst because of their unique properties due to the high le...

The effect of multidimensional heterostructures on charge transfer and charge separation is intriguing in photocatalytic applications. Herein, NiS/ZnIn2S4 heterostructures with tailorable composition, tunable light absorption, and controllable band gap were successfully prepared by a two-step method to show uniform NiS nanoparticles with an average size of 10 nm loaded homogeneously on porous ZnIn2S4 nanosheets. Consequently, NiS/ZnIn2S4 heterostructures have markedly enhanced light absorption and efficient photocatalytic efficiency, reaching the hydrogen evolution rate of 5.0 μmol h−1 under the light irradiation at 420 nm, to be approximately three times higher than that of pure ZnIn2S4. The enhanced photocatalytic efficiency results from faster charge transfer and more efficient photogenerated electron-hole separation under beneficial band alignment. The results shed light on how the photocatalytic reaction occurs at the interface between NiS and ZnIn2S4, and can open a new avenue for synthesizing efficient photocatalysts.

Examination of the spectral and kinetic characteristics of charge carrier recombination on nanostructured semiconductors by photoluminescence (PL) plays a significant role in understanding the photocatalytic process. Here, with an in situ single-particle PL technique, we studied the transport behavior of charge carriers in individual one-dimensional (1D) core-shell structures of CdS@CuS nanowires. Through the PL intensity changes in the single-particle PL spectroscopy, effective interfacial electron transport along the interface of CdS and CuS was observed, which contributes to the significant improvement (i.e., 13.5-fold increase) of photocatalytic H2 production compared to that for pure CdS nanowires. The present study provides visual experimental evidence for understanding restraining of charge carrier recombination in the semiconductor.

Wide absorption from the ultraviolet (UV) to near-infrared (NIR) region and enhanced charge separation are two main requirements for promising semiconductor photocatalysts. Here, we studied visible...

Gaseous atmosphere during graphitic carbon nitride (g-C3N4) preparation can have a significant influence on modifying the morphological texture, polymeric structure, charge carrier behavior, and consequently the photocatalytic performance. Herein, we developed a new one-step method to fabricate g-C3N4 through direct pyrolysis of 3-amino-1,2,4-triazole in CO2 atmosphere (C3N4-T-CO2) with no additive. Surprisingly, the H2 production activity of C3N4-T-CO2 photocatalyst under visible light irradiation was 2.4 and 1.7 times as high as that of g-C3N4 obtained under air and N2 atmosphere with the same heating process, respectively. Detailed characterizations indicated that the CO2 calcination atmosphere induced less nitrogen vacancies with no charge transport ability, more NHx groups, and faster rate of the electron transport between heptazine rings for C3N4-T-CO2 among three samples. It is also suggested that the larger number of NHx in C3N4-T-CO2 could enhance the interlayer electron transport through the hydrogen-bonding interaction between C3N4 layers. Time-resolved photoluminescence, single-particle fluorescence, and femtosecond time-resolved transient absorption measurements were performed to elucidate the efficient charge transfer and trapping processes in C3N4-T-CO2. For the first time, such unprecedented effect of CO2 calcination atmosphere was observed for g-C3N4. This work not only presents a promising strategy in designing highly effective g-C3N4 photocatalyst for solar energy conversion, but also makes an insight into the charge transfer process in g-C3N4 photocatalyst.

The introduction of nitrogen (N) defects (N vacancies labeled as Vns and cyano groups) has been demonstrated as one of the promising strategies to extend the light absorption range of graphitic carbon nitride (CN), thus improving the photocatalytic activity for hydrogen (H2) evolution. However, the photocatalysis mechanism of such N-deficient CN (DCN) has not been fully understood. In this study, N defects are introduced into CN by a KOH-assisted thermal polymerization method. On the basis of experimental investigations and density functional theory (DFT) calculations, it is found that the extension of the absorption range of DCN is attributed to both the valence band (VB) tailing induced by Vns and bandgap narrowing induced by cyano groups. Moreover, the conduction band (CB) is lowered by the N defects, indicating a reduced driving force for H2 evolution. Transient absorption (TA) spectroscopy reveals that when the electrons in the intrinsic VB of DCN are excited to the CB, the separation efficiency of these electrons and as-generated holes is seriously restricted by their low mobility. While when the electrons in VB tail states (Vn states) are excited to the CB, the separation efficiency of these electrons and as-generated holes could be almost maintained thanks to the improved mobility of the holes. As a result, DCN shows a limited enhancement of the H2 evolution rate compared with CN under visible light irradiation. This work points out that extending the light absorption range of a given photocatalyst by doping (or self-doping) may be accompanied by some negative factors, which restrict the overall photocatalytic activity.

Au TNP/g-C3N4 as a plasmonic photocatalyst for H2 production under NIR light irradiation was investigated by finite-difference time-domain (FDTD) simulations and time-resolved transient absorption measurements, revealing enhanced H2 production owing to a stronger electromagnetic field in Au TNP/g-C3N4 and plasmon-induced hot electron transfer from Au TNPs to g-C3N4.

Functional nucleic acids with the capability of generating fluorescence in response to hybridization events, microenvironment or structural changes are valuable as structural probes and chemical sensors. We now demonstrate the enzyme-assisted preparation of nucleic acids possessing multiple thiazole orange (TO) dyes and their fluorescent behavior, that show a spectral change from the typical monomer emission to the excimer-type red-shifted emission. We found that the fluorescent response and emission wavelength of the TO dyes were dependent on both the state of the DNA structure (single- or double-stranded DNA) and the arrangement of the TO dyes. We showed that the fluorescent behavior of the TO dyes can be applied for the detection of RNA molecules, suggesting that our approach for preparing the fluorescent nucleic acids functionalized with multiple TO dyes could be useful to design a fluorescence bioimaging and detection technique of biomolecules.

The development of photocatalysts is an essential task for clean energy generation and establishing a sustainable society. This paper describes the aggregation-induced photocatalytic activity (AI-PCA) of amphiphilic rhodamines and photocatalytic functions of the supramolecular assemblies. The supramolecular assemblies consisting of amphiphilic rhodamines with octadecyl alkyl chains exhibited significant photocatalytic activity under visible light irradiation in water, while the corresponding monomeric rhodamines did not exhibit photocatalytic activity. The studies on the photocatalytic mechanism by spectroscopic and microscopic analyses clearly demonstrated the AI-PCA of the rhodamines. Moreover, the supramolecular assemblies of the rhodamines exhibited excellent photocatalytic hydrogen evolution rates (up to 5.9 mmol g−1 h−1)., Simple amphiphilic rhodamines formed supramolecular assemblies and exhibited aggregation-induced photocatalytic activity and hydrogen evolution in water.

The concept of aromaticity is essential for chemists to understand the nature of many chemical substances. “In-plane” aromaticity is a unique type of aromaticity found in some π-conjugated systems consisting of radially oriented p-orbitals. Although in-plane aromaticity has been theoretically predicted about 40 years ago, its intrinsic properties are much less well understood than those of conventional Hückel aromatic systems with perpendicularly oriented p-orbitals because of lack of available examples of in-plane aromatic molecules. Here we demonstrate, from both theoretical and experimental aspects, that in-plane aromaticity of cycloparaphenylenes is reversed upon excitation to the lowest triplet state. In-plane non-aromatic neutral forms with a 4N-electron system and in-plane aromatic dications with a 4N+2-electron system turn out to be aromatic and anti-aromatic, respectively, indicating that Baird’s rule holds for the in-plane aromatic system. Armchair carbon nanotube fragments based on the cycloparaphenylene were also found to follow Baird’s rule from a magnetic viewpoint.

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We investigate the photogenerated electron kinetics of a thermal-decomposed polymeric carbon nitride (TCN) synthesized in air using femtosecond time-resolved diffuse reflectance spectroscopy. We find that the oxygen functional groups in TCN contribute to the formation of reactive shallow trap states for photogenerated electrons, leading to an enhanced activity for photocatalytic hydrogen evolution.

Hard X-ray excited optical luminescence is a unique property of materials, which makes them promising for biological imaging applications. However, the preparation of biocompatible contrast agents for hard X-ray excited optical luminescence remains a considerable challenge that has, to date, not been overcome. In this study, we investigated the luminescence properties of protein-directed Au

Graphitic carbon nitride (g-C3N4) is a promising visible-light-driven photocatalyst for solar energy conversion by splitting water into H2. However, the photocatalytic performance of g-C3N4 is not sufficient because of low surface area and fast recombination of charge carriers. Here, g-C3N4 with nanosheet structure was prepared by using mixture of melamine (M) and urea (U) as the precursors for the photocatalytic H2 production from water. The use of U increased the surface area with mesoporous structure and defects of nitrogen vacancies acting as trap states in g-C3N4. The as-obtained g-C3N4-M1U2 (1 and 2 denote the weight ratios of M and U, respectively) exhibited the photocatalytic H2 production rate of 3.1 mmol g−1 h−1 under λ ≥ 400 nm light irradiation and apparent quantum efficiency (AQE) of 74% at λ = 400 nm. Single-particle photoluminescence (PL), originated from charge recombination of photogenerated charge carriers, showed longer lifetime of charge carriers in g-C3N4-M1U2 than that in g-C3N4-M. Femtosecond time-resolved diffuse reflectance measurement was performed to observe the photogenerated electrons trapping in g-C3N4-MxUy. The results show that the electron trapping by the defects as trap states occurs faster in g-C3N4-MxUy than in g-C3N4-M. It is suggested that the use of U increases the defects as electron trap states, leading efficient photocatalytic H2 production.

Photocatalytic water reduction into H2 provides huge charm for simultaneously resolving fossil energy shortage and environmental issues. Seeking photocatalysts with characteristics of low-cost, environmental friendliness and visible light response, and accelerating the charge separation remain significant challenges to develop high efficient solar-to-H2 conversion systems. Here, quaternary sulfur semiconductor Zn0.4Ca0.6In2S4 (ZCIS) microspheres composed of cross-linked nanosheets and ZCIS microspheres modified with MoS2 (ZM-X) were designed and prepared via hydrothermal methods. Detailed characterizations indicated that the layer structured MoS2 nanosheets were mainly deposited on the surface of ZCIS nanosheet to form a 2D-2D structure that greatly increased the contact surface area for charge transfer, which was critical to the high photocatalytic performance for H2 evolution. Femtosecond time-resolved diffuse reflectance spectroscopy was used to evaluate the transfer dynamics of photogenerated electrons in ZCIS and ZM-X and revealed that an additional decay route within 5 ps for the photogenerated electrons in ZCIS after combining with MoS2 appeared which could be ascribed to the electron injection from ZCIS to MoS2. In addition, it was also demonstrated that ZM-3.0 (ZCIS with 3 wt% MoS2 loading amount) exhibited the fastest electron injection within only 1.12 ps and the highest efficient injection efficiency of 69.9%. As a result, ZM-3.0 exhibited the evolution rate of 3.5 μmol h-−1 under visible light irradiation (λ ≥ 420 nm), which was 27 times higher than that of ZCIS (0.13 μmol h−1). The results indicate that the quaternary sulfur semiconductor has great potential as a new kind of photocatalysts for solar energy conversion.

Tetraphenylporphyrinatophosphorus(V) complexes (1) comprising two axially linked benzylidene imidazolone (Biz) moieties, which are chromophores of the green fluorescent protein, were prepared. In medical applications such as photodynamic therapy, the P-porphyrin part (Ptp) is expected to sensitize to generate singlet oxygen, whereas the Biz units act as fluorescent probes. The fluorescence spectra of 1 were analyzed under the excitations of Biz at 370 nm. Fluorescence stemming from the excited states of Biz and Ptp was observed at 460 and 610 nm, respectively. The intramolecular quenching of Biz in the excited singlet state by Ptp occurred, resulting in weak fluorescence from Biz. The introduction of a cyano group in the Biz units of 1 enhanced their fluorescence quantum yield up to 7.7 × 10−4. The fluorescence spectra of 1 under the excitations of Ptp at 550 nm were extremely similar to that of a reference compound of P-porphyrin without the Biz chromophore, dimethoxy(tetraphenylporphyrinato)phosphorus chloride. The physicochemical parameters of Ptp remained unaltered following the introduction of Biz on the axial positions of P-porphyrin.

Silver phosphate (Ag3 PO4 ) is a promising visible-light-driven photocatalyst with a strong oxidation power and exceptionally high apparent quantum yield of O2 evolution. Although engineering Ag3 PO4 facets is widely known to enhance its photocatalytic activity, most studies have explained its facet effect by calculating surface energies. Herein, the charge carrier dynamics in three kinds of Ag3 PO4 crystals (mixed facets, cubic, and tetrahedral structures) were first investigated using single-particle photoluminescence microscopy and femtosecond time-resolved diffuse reflectance spectroscopy. As a result, we clarified that the disagreement between the photocatalytic activities (dye degradation and O2 evolution) of different Ag3 PO4 facets are the consequence of trade-off between catalytic activity and lifetime of photogenerated charge carriers in addition to surface energy.

出版時に修正箇所あり, 出版時のタイトル：Donor–Donor′–Acceptor Triads Based on [3.3]Paracyclophane with a 1,4‐Dithiafulvene Donor and a Cyanomethylene Acceptor: Synthesis, Structure, and Electrochemical and Photophysical Properties