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A control survey technique using a laser tracker and a digital level was introduced to the KEK e−/e+ injector linac in 2020. Control surveys are continuously demonstrated during the machine's downtimes every summer. Analysis of the two-year data reproduces their trends in terms of the fiducial points on the beam line. In our paper, we report on systematic coordinates and their error distributions evaluated by a control survey, compare them with a numerical survey simulation, and discuss newly encountered issues. [ABSTRACT FROM AUTHOR]

Perfluoroalkyl substances (PFASs) and fluorinated polymers (FPs) have been extensively utilized in various industries, whereas their extremely high stability poses environmental persistence and difficulty in waste treatment. Current decomposition approaches of PFASs and FPs typically require harsh conditions such as heating over 400 °C. Thus, there is a pressing need to develop a new technique capable of decomposing them under mild conditions. Here, we demonstrated that perfluorooctanesulfonate (PFOS), known as a "persistent chemical," and Nafion, a widely utilized sulfonated FP for ion-exchange membranes, can be efficiently decomposed into fluorine ions under ambient conditions via the irradiation of visible LED light onto semiconductor nanocrystals (NCs). PFOS was completely defluorinated within 8-h irradiation of 405-nm LED light, and the turnover number of the C-F bond dissociation per NC was 17200. Furthermore, 81 % defluorination of Nafion was achieved for 24-h light irradiation, demonstrating the efficient photocatalytic properties under visible light. We revealed that this decomposition is driven by cooperative mechanisms involving light-induced ligand displacements and Auger-induced electron injections via hydrated electrons and higher excited states. This study not only demonstrates the feasibility of efficiently breaking down various PFASs and FPs under mild conditions but also paves the way for advancing toward a sustainable fluorine-recycling society., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Stepwise two-photon absorption processes have received considerable attention, especially in photocatalysis, due to their relatively lower power threshold, characteristic spatial selectivity, amplification of chemical reactions, and so on. Meanwhile, studies on the relaxation dynamics of higher excited states in condensed systems have been limited for several molecular systems due to the short-lived nature of these states. In this study, we synthesized perylene-substituted perylene bisimide (PBI) and its derivate as model compounds and investigated their excited-state dynamics, including higher excited states, using pump-repump-probe spectroscopy. We revealed that these molecules form charge-transfer (CT) states instantaneously after the excitation, regardless of whether it is the perylene moiety or the PBI moiety that is excited. The lifetime of the CT state was shorter when the distance between the donor (perylene) and the acceptor (PBI) was shorter. Moreover, we also revealed that a higher-lying CT state generated by the stepwise excitation of the CT state using a 740-nm pulse induced Stark effect to the neighboring perylene moiety. The Stark effect not only gives more detailed information about the CT state, but also presents the possibility of new photofunctions, such as instantaneous modulation of the electronic state to achieve optimal electronic properties. These insights contribute to understanding advanced photochemical reactions and would be important for exploring photocatalytic reactions involving higher excited states., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

We herein report photodoping and thereby photochromism of semiconductor nanocrystals under air in a temperature-responsive supramolecular gel and its back reactions induced by direct heating or near-infrared photothermal conversion. We also present their application to the spatiotemporal patterning of photoluminescence.

Nonlinear photochromic reactions that work with weak incoherent light are important for molecular operations with high spatial resolution and multiple photofunctions based on single molecules. However, nonlinear photochromic compounds generally require complex molecular design, restricting accessibility in various fields. Herein, we report nonlinear photochromic properties in a perylene-substituted rhodamine spirolactam derivative (Rh-Pe), which is synthesized from rhodamine B in facile procedures. Direct excitation of Rh-Pe produces the triplet excited state via the charge-transfer (CT) state. The triplet excited state causes triplet-triplet annihilation to bring the generation of the intensely colored ring-open form with nonlinear behavior. Furthermore, green- and red-light-induced photochromism was achieved in Rh-Pe using triplet sensitizers, although Rh-Pe can be directly excited only by ultraviolet and blue light. Our findings are expected to contribute to the development of photofunctional materials showing nonlinear behavior and low-energy light responsivity., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Organic ligands on the surface of nanocrystals (NCs) are extremely important in influencing various physical properties, such as dispersibility, electrical properties, and optical properties. Recent studies have revealed that a slight difference in the molecular structure of aliphatic organic ligands significantly affects the dispersibility of the NCs. On the other hand, the effects of the difference in the molecular structure of ligands on the excited-state dynamics of NCs remain elusive. In this study, we synthesized a series of colloidal ZnO NCs capped with different alkyl phosphonic acids and investigated their photophysical properties using emission decay measurements and transient absorption spectroscopy. The spectral shape and lifetime of the emission originating from the surface oxygen defects of ZnO NCs are almost the same irrespective of the alkyl phosphonic ligands used, indicating that the electronic states of the surface oxygen defects are not affected by the bulkiness of the ligand. On the other hand, the emission quantum yield correlates with the rate of carrier trapping by oxygen defects, suggesting that the rate of carrier trapping reflects the number of oxygen defects. Revealing the detailed relationship between molecular structures of organic ligands and the optical properties of NCs is important for advanced photofunctional superstructures using semiconductor NCs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Photochromic reactions of the phenoxyl-imidazolyl radical complex (PIC), which is one of the rate-tunable fast T-type photoswitches, dramatically change by the introduction of bulky substituents around the photochromic units. While these substituents are expected to affect the initial bond dissociation processes, they have not been elucidated yet. Here, we revealed the ultrafast bond dissociation processes of PIC derivatives with different bulky substituents by subpicosecond to nanosecond transient absorption spectroscopy. We revealed that the bulky substituents around the photochromic units decelerate the bond dissociation processes, whereas they largely accelerate the thermal back reactions of the photogenerated open-ring isomer. Moreover, we found clear correlations between the formation kinetics of the open-ring isomer and molecular structural changes. The initial bond-dissociation process dictates the products and the efficiency of photochromic reactions. Therefore, revealing these processes is important not only for fundamental photochemistry but also for optimizing photochromic properties for advanced functional materials.

We demonstrate that the phenoxyl-imidazolyl radical complex (PIC), which is a rate-tunable fast photoswitch, can be used as a ligand that directly coordinates with iridium (III) ions. The iridium complexes show the characteristic photochromic reactions originating from the PIC moiety, whereas the behaviour of transient species is substantially different from that of the PIC.

A control survey technique using a laser tracker and a digital level was introduced to the KEK e-/e+ injector linac in 2020. Control surveys are continuously demonstrated during the machine's downtimes every summer. Analysis of the two-year data reproduces their trends in terms of the fiducial points on the beam line. In our paper, we report on systematic coordinates and their error distributions evaluated by a control survey, compare them with a numerical survey simulation, and discuss newly encountered issues., (© 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).)

Dithienylnitrophenols were synthesized as precursors of π-electronic anions, which were stabilized by intramolecular chalcogen bonding, forming various ion pairs in combination with cations. The modes of solid-state charge-by-charge assemblies, along with solution-state stacking and photoinduced electron transfer behaviors, were modulated by the constituent ionic species.

The optical property of an ionic metal nanocluster (NC) is affected by the ionic interaction with counter ions. Here, we report that the modification of trianionic [Ag 29 (BDT) 12 (TPP) 4 ] 3- NC (BDT: 1.3-benzenedithiol; TPP: triphenylphosphine) with silver(I) complexes led to the intense photoluminescence (PL) in the near-infrared (NIR) region. The binding of silver(I) complexes to the peripheral region of Ag 29 NC is confirmed by the single-crystal X-ray diffraction (SCXRD) measurement, which is further supported by electrospray ionization mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR) spectroscopy. The change of excited-state dynamics by the binding of silver(I) complexes is discussed based on the results of a transient absorption study as well as temperature-dependent PL spectra and PL lifetime measurements. The modification of Ag 29 NCs with cationic silver(I) complexes is considered to give rise to a triplet excited state responsible for the intense NIR PL. These findings also afford important insights into the origin of the PL mechanism as well as the possible light-driven motion in Ag 29 -based NCs.

Porphyrin ion pairs, the charge of which is delocalized in core units, form tightly associated structures through i π- i π interactions. 5,10,15-Triphenyl-substituted porphyrin-Au III complex, which is favorable for forming stacked structures in the form of a stable ion, has been synthesized. Ion-pair metathesis based on the hard and soft acids and bases theory enabled combination with porphyrin anions possessing electronic states controlled by electron-donating and electron-withdrawing groups. Transient absorption spectroscopy suggested that the lifetimes of the radical pairs generated by photoinduced electron transfer of the ion pairs could be controlled by a judicious combination of the anions and cations., (© 2023 Wiley-VCH GmbH.)

π-Electronic ion pairs are of interest for fabricating electronic materials that use intermolecular interactions based on electrostatic and dispersion forces, defined as i π- i π interactions, to provide dimension-controlled assemblies. Porphyrin ions, whose charge is delocalized in the core units, are suitable for ordered arrangement and assemblies by ion pairing. Herein, charged porphyrins were found to form solid-state assemblies and solution-state stacked ion pairs according to the peripheral electron-donating groups (EDGs) and electron-withdrawing groups (EWGs). The concentration-dependent 1 H NMR signal shifts of a porphyrin ion pair, comprising a meso -EWG cation and a meso -EWG anion, provided a hetero-dimerization constant of 2.8 × 10 5 M -1 in CD 2 Cl 2 at 20 °C. In the ion pair of a meso -EWG cation and a meso -EDG anion, the electron transfer in the steady and excited states according to solvent polarity and photoexcitation, respectively, produced the radical pairs. The electron spin resonance analysis in frozen toluene revealed the formation of a heterodiradical in a closely stacked structure by the antiferromagnetic dipolar interaction and temperature-dependent spin transfer behavior.

Anion-responsive sign inversion of circularly polarized luminescence (CPL) was successfully achieved by N 3 O 6 -type nona-coordinated europium(III) (Eu 3+ ) complexes [( R )- 1 and ( S )- 1 ] composed of a less-hindered unsymmetrical N 3 -tridentate ligand (a chiral bis(oxazoline) ligand) and three O 2 -chelating (β-diketonate) ligands. Here, ( R )- 1 exhibited a positive CPL signal ( I L - I R > 0) at the 5 D 0 → 7 F 1 transition of Eu 3+ , which can be changed to a negative sign (i.e., I L - I R > 0 → I L - I R < 0) by the coordination of trifluoroacetic anions (CF 3 COO - ) to the Eu 3+ center. However, ( R )- 1 preserved the original positive CPL signal (i.e., I L - I R > 0 → I L - I R > 0) in the presence of a wide range of competing anions (Cl - , Br - , I - , BF 4 - , ClO 4 - , ReO 4 - , PF 6 - , OTf - , and SbF 6 - ). Thus, ( R )- 1 acts as a smart target identifiable probe, where the CPL measurement ( I L - I R ) can distinguish the signals from the competing anions (i.e., I L - I R < 0 vs I L - I R > 0) and eliminate the background emission (i.e., I L - I R = 0) from the background emitter (achiral luminescent compounds). The presented approach is also promising in terms of bio-inspired optical methodology because it enables nature's developed chiral sensitivity to use circularly polarized light for object identification (i.e., I L - I R = 0 vs | I L - I R | > 0).