Relaxation dynamics of higher excited states of perylene-substituted perylene bisimide derivatives.

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.

Multiphoton-Driven Photocatalytic Defluorination of Persistent Perfluoroalkyl Substances and Polymers by Visible Light.

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.

Photodoping-based broadband photochromism of semiconductor nanocrystals under air operated by a supramolecular gel.

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.

A Nonlinear Photochromic Reaction Based on Sensitizer-Free Triplet-Triplet Annihilation in a Perylene-Substituted Rhodamine Spirolactam.

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.

Effect of the bulkiness of alkyl ligands on the excited-state dynamics of ZnO nanocrystals.

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.

Unraveling Steric Effects on Ultrafast Bond-Dissociation Processes of Photochromic Radical Complexes.

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.

Photochromic dinuclear iridium(III) complexes having phenoxyl-imidazolyl radical complex derivatives.

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.

Excited State Engineering in Ag29 Nanocluster through Peripheral Modification with Silver(I) Complexes for Bright Near-Infrared Photoluminescence.

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 [Ag29(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 Ag29 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 Ag29 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 Ag29-based NCs.

Ion-Pairing Assemblies of Dithienylnitrophenol-Based π-Electronic Anions Stabilized by Intramolecular Interactions.

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.

Substituent-Dependent Photoexcitation Processes of π-Stacked Ion Pairs.

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-AuIII 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.

π-Stacked Ion Pairs: Tightly Associated Charged Porphyrins in Ordered Arrangement Enabling Radical-Pair Formation.

π-Electronic ion pairs are of interest for fabricating electronic materials that use intermolecular interactions based on electrostatic and dispersion forces, defined as iπ-iπ 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 1H 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 × 105 M-1 in CD2Cl2 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-Driven Circularly Polarized Luminescence Inversion of Unsymmetrical Europium(III) Complexes for Target Identifiable Sensing.

Anion-responsive sign inversion of circularly polarized luminescence (CPL) was successfully achieved by N3O6-type nona-coordinated europium(III) (Eu3+) complexes [(R)-1 and (S)-1] composed of a less-hindered unsymmetrical N3-tridentate ligand (a chiral bis(oxazoline) ligand) and three O2-chelating (ß-diketonate) ligands. Here, (R)-1 exhibited a positive CPL signal (IL - IR > 0) at the 5D0 → 7F1 transition of Eu3+, which can be changed to a negative sign (i.e., IL - IR > 0 → IL - IR < 0) by the coordination of trifluoroacetic anions (CF3COO-) to the Eu3+ center. However, (R)-1 preserved the original positive CPL signal (i.e., IL - IR > 0 → IL - IR > 0) in the presence of a wide range of competing anions (Cl-, Br-, I-, BF4-, ClO4-, ReO4-, PF6-, OTf-, and SbF6-). Thus, (R)-1 acts as a smart target identifiable probe, where the CPL measurement (IL - IR) can distinguish the signals from the competing anions (i.e., IL - IR < 0 vs IL - IR > 0) and eliminate the background emission (i.e., IL - IR = 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., IL - IR = 0 vs | IL - IR | > 0).

Helix-mediated over 1 nm-range chirality recognition by ligand-to-ligand interactions of dinuclear helicates.

Long-range chirality recognition between the two chiral guest ligands can be tuned based on the helix distances (d Ln-Ln = 11.5 and 14.0 Å) of bis-diketonate bridged dinuclear lanthanide complexes (2Th and 3Th, respectively) used as mediators. Both 2Th and 3Th form one-dimensional (1D) helical structures upon terminal binding of two chiral guest co-ligands (L R or L S ). Long-range chiral self-recognition is achieved in self-assembly of 2Th with L R and L S to preferentially form homochiral assemblies, 2Th-L R ·L R and 2Th-L S ·L S , whereas there is no direct molecular interaction between the two guest ligands at the terminal edges. X-ray crystal structure analysis and density functional theory studies reveal that long-range chiral recognition is achieved by terminal ligand-to-ligand interactions between the bis-diketonate ligands and chiral guest co-ligands. Conversely, in self-assembly of 3Th with a longer helix length, statistical binding of L R and L S occurs, forming heterochiral (3Th-L R ·L S ) and homochiral (3Th-L R ·L R and 3Th-L S ·L S ) assemblies in an almost 1 : 1 ratio. When phenyl side arms of the chiral guest co-ligands are replaced by isopropyl groups (L' R and L' S ), chiral self-recognition is also achieved in the self-assembly process of 3Th with the longer helix length to generate homochiral (3Th-L' R ·L' R and 3Th-L' S ·L' S ) assemblies as the favored products. Thus, subtle modification of the chiral guests is capable of achieving over 1.4 nm-range chirality recognition.

Structure Determination of Europium Complexes in Solution Using Crystal-Field Splitting of the Narrow f-f Emission Lines.

Nine nona-coordinated Eu(III) complexes (1-9) studied here have three unsymmetric ß-diketonate ligands and one chiral Ph-Pybox ligand, which can produce eight possible coordination isomers, depending on the position of the three unsymmetric ß-diketonate ligands. Substituents on the ß-diketonate ligands cause a rational structural rearrangement upon crystallization. Substituents with higher polarity, including -CN, -F, -Cl, -Br, -OMe, and -OEt, employ intercomplex hydrogen bonding to generate an association complex through structural rearrangement upon crystallization. Substituents with lower polarity, including -CF3, -SMe, and -Me, cause the most energetically favorable isomer to crystallize directly from solution. These two crystal structures exhibit well-resolved f-f emission lines with characteristic Stark splitting structures. This work revealed that the configuration of the Eu(III) complexes in solution can be determined by systematic comparison of their Stark splitting structures to those obtained from the solid phase using density functional theory (DFT)-based predictions combined with circular dichroism data.

Visible Circularly Polarized Luminescence of Octanuclear Circular Eu(III) Helicate.

This work reports on the structural and photophysical characterization of D4-symmetrical octanuclear circular LnIII helicates, [(R)- or (S)-iPr-Pybox]8(LnIII)8(THP)8 (where Ln = Eu and Tb, THP = trianionic tris-ß-diketonate, and iPr-Pybox = chiral bis(4-isopropyl-2-oxazolinyl)pyridine). X-ray crystallographic analysis revealed that the octanuclear circular helicate possesses square antiprism architecture and consists of four [(R)- or (S)-iPr-Pybox]2LnIII2(THP)2 asymmetric units arranged in a closed ring form. Ligand-to-ligand interactions between the THP and the iPr-Pybox ligands have successfully directed formation of enantiopure, homoconfigurational (Δ,Δ,Δ,Δ,Δ,Δ,Δ,Δ)-R and (Λ,Λ,Λ,Λ,Λ,Λ,Λ,Λ)-S isomers. All of the nonacoordinated LnIII ions are identical and exhibit a distorted capped square antiprism (CSAP) geometry. Upon excitation of the ligand absorption band (λ = 360 nm), the circular helicates display characteristic EuIII (red, 5D0 → 7FJ, J = 0-4) or TbIII (green, 5D4 → 7FJ, J = 6-3) core f-f luminescence. The overall emission quantum yields of the circular EuIII and TbIII helicates are 0.145 and 0.0013, respectively, in chloroform. The EuIII and TbIII complexes exhibit remarkable circularly polarized luminescence (CPL) activity at their magnetic dipole transition with observed luminescence dissymmetry factors |glum| of 1.25 (5D0 → 7F1, λ = 592 nm) and 0.25 (5D4 → 7F5, λ = 541 nm), respectively. Exceptional |glum| values of the circular EuIII helicates highlight the visible intensity difference between left and right circularly polarized emissions of R and S isomers in chloroform and PMMA thin film.

Design and Synthesis of Cyclometalated Iridium(III) Complexes-Chromophore Hybrids that Exhibit Long-Emission Lifetimes Based on a Reversible Electronic Energy Transfer Mechanism.

We report on the design and synthesis of triscyclometalated iridium (Ir) complexes that contain aryloxy groups at the end of diamino linkers, which exhibit an extraordinarily long-emission lifetime, and were prepared by regioselective substitution reactions of fac-tris-homoleptic cyclometalated Ir complexes, fac-Ir(tpy)3 (tpy = 2-(4'-tolyl)pyridine). It was found that the Ir(tpy)3 complex, equipped with approximately one to six 6-N,N-dimethylamino-2-naphthoic acid (DMANA) groups through the appropriate alkyl linkers, exhibited remarkably long-emission lifetimes of up to 216 µs in DMSO/H2O at room temperature through a reversible electronic energy transfer effect between the Ir complex core and the organic chromophore moieties; however, under the same conditions, the lifetime of fac-Ir(tpy)3 was 1.4 µs. Regarding the mechanistic aspects, the relationship between the emission lifetimes of the Ir complexes and the structures and numbers of the conjugated chromophores, linker lengths, solvents, positions of the chromophores on the Ir(tpy)3 core, and related items are discussed.

Significant Enhancement of Absorption and Luminescence Dissymmetry Factors in the Far-Red Region: A Zinc(II) Homoleptic Helicate Formed by a Pair of Achiral Dipyrromethene Ligands.

A homoleptic zinc(II) helicate organized by a pair of achiral dipyrromethene ligands through zinc(II) coordination was synthesized to evaluate the chiroptical properties. This zinc complex showed strong exciton-coupled chiroptical responses from the helical configuration with a large absorption dissymmetry factor |gabs | (up to 0.20). More importantly, intense polarized luminescence in the far-red region (700-850 nm) with a fluorescence quantum yield ΦFL of 0.23 was observed for this helicate with a dissymmetry factor |glum | of 0.022, the largest value among rare-earth- and precious-metal-free small molecules. These unprecedentedly large g values were supported by theoretical calculations.

The effect of ligand symmetry on the ratiometric luminescence characteristics of lanthanides.

This work demonstrated that the ligand symmetry of europium(iii) complexes controls the ratiometric luminescence characteristics of lanthanides. Nona-coordinated europium(iii) complexes having unsymmetrical ß-diketonate ligands (Cs) exhibit distinctive ratiometric spectral variations in the extremely narrow f-f transition bands over the temperature range from 253 to 323 K. In contrast, no such ratiometric change can be observed in a series of nona-coordinated europium(iii) complexes containing symmetrical ß-diketonate ligands (C2v). The remarkable difference depending on the ligand symmetry (Csvs. C2v) suggests that the coordination rearrangement of ß-diketonate in the complex causes ratiometric spectral variations in extremely narrow f-f transition bands, where two europium(iii) complex isomers exist in the solution equilibrium. A self-calibration method using dual iso-emissive points is reported, where self-calibration using the two emission intensities at the iso-emissive points reduces the coefficient of variation in luminescence thermometry.