Relationship between spatially heterogeneous reaction dynamics and photochemical kinetics in single crystals of anthracene derivatives.

Understanding physicochemical property changes based on reaction kinetics is required to design materials exhibiting desired functions at arbitrary timings. In this work, we investigated the photodimerization of anthracene derivatives in single crystals. Single crystals of 9-cyanoanthracene (9CA) and 9-anthraldehyde (9AA) exhibited reaction front propagation on the optical length scale, while 9-methylanthracene and 9-acetylanthracene crystals underwent spatially homogeneous conversion. Moreover, the sigmoidal behavior in the absorbance change associated with the reaction was much pronounced in the case of 9CA and 9AA and correlated with the observation of heterogeneous reaction progress. A kinetic analysis based on the Finke-Watzky model showed that the effective quantum yield of the photochemical reaction changes by more than an order of magnitude during the course of the reaction in 9CA and 9AA. Both the reaction front propagation and nonlinear kinetic behavior could be rationalized in terms of the difference in the cooperativity of the reactions. We propose a plausible mechanism for the heterogeneous reaction progress in single crystals that depends on the magnitude of the conformational change required for reaction. Our results provide useful information to understand the connection between photochemical reaction progress in the crystalline phase and the dynamic changes in the physicochemical properties

Near-infrared two-photon absorption and excited state dynamics of a fluorescent diarylethene derivative

The version of record of this article, first published in Photochemical and Photobiological Sciences, is available online at Publisher’s website: https://doi.org/10.1007/s43630-024-00573-y.Abstract: Near-infrared two-photon absorption and excited state dynamics of a fluorescent diarylethene (fDAE) derivative were investigated by time-resolved absorption and fluorescence spectroscopies. Prescreening with quantum chemical calculation predicted that a derivative with methylthienyl groups (mt-fDAE) in the closed-ring isomer has a two-photon absorption cross-section larger than 1000 GM, which was experimentally verified by Z-scan measurements and excitation power dependence in transient absorption. Comparison of transient absorption spectra under one-photon and simultaneous two-photon excitation conditions revealed that the closed-ring isomer of mt-fDAE populated into higher excited states deactivates following three pathways on a timescale of ca. 200 fs: (i) the cycloreversion reaction more efficient than that by the one-photon process, (ii) internal conversion into the S1 state, and (iii) relaxation into a lower state (S1’ state) different from the S1 state. Time-resolved fluorescence measurements demonstrated that this S1’ state is relaxed to the S1 state with the large emission probability. These findings obtained in the present work contribute to extension of the ON–OFF switching capability of fDAE to the biological window and application to super-resolution fluorescence imaging in a two-photon manner

Doubly linked chiral phenanthrene oligomers for homogeneously π-extended helicenes with large effective conjugation length

Helically twisted conductive nanocarbon materials are applicable to optoelectronic and electromagnetic molecular devices working on the nanometer scale. Herein, we report the synthesis of per-peri-perbenzo[5]- and [9]helicenes in addition to previously reported π-extended [7]helicene. The homogeneously π-extended helicenes can be regarded as helically fused oligo-phenanthrenes. The HOMO−LUMO gap decreased significantly from 2.14 to 1.15 eV with increasing helical length, suggesting the large effective conjugation length (ECL) of the π-extended helical framework. The large ECL of π-extended helicenes is attributed to the large orbital interactions between the phenanthrene subunits at the 9- and 10-positions, which form a polyene-like electronic structure. Based on the experimental results and DFT calculations, the ultrafast decay dynamics on the sub-picosecond timescale were attributed to the low-lying conical intersection

Object Transportation System Mimicking the Cilia of Paramecium aurelia Making Use of the Light-Controllable Crystal Bending Behavior of a Photochromic Diarylethene

The design of an object transportation system exploiting the bending behavior of surface-assembled diarylethene crystals is reported. A photoactuated smart surface based on this system can transport polystyrene beads to a desired area depending on the direction of the incident light. Two main challenges were addressed to accomplish directional motion along a surface: first, the preparation of crystals whose bending behavior depends on the direction of incident light; second, the preparation of a film on which these photochromic crystal plates are aligned. Nuclei generation and nuclear growth engineering were achieved by using a roughness-controlled dotted microstructured substrate. This system demonstrates how to achieve a mechanical function as shown by remote-controlled motion along a surface

Real-time observation of X-ray-induced intramolecular and interatomic electronic decay in CH2I2

The increasing availability of X-ray free-electron lasers (XFELs) has catalyzed the development of single-object structural determination and of structural dynamics tracking in realtime. Disentangling the molecular-level reactions triggered by the interaction with an XFEL pulse is a fundamental step towards developing such applications. Here we report real-time observations of XFEL-induced electronic decay via short-lived transient electronic states in the diiodomethane molecule, using a femtosecond near-infrared probe laser. We determine the lifetimes of the transient states populated during the XFEL-induced Auger cascades and find that multiply charged iodine ions are issued from short-lived (similar to 20 fs) transient states, whereas the singly charged ones originate from significantly longer-lived states (similar to 100 fs). We identify the mechanisms behind these different time scales: contrary to the short-lived transient states which relax by molecular Auger decay, the long-lived ones decay by an interatomic Coulombic decay between two iodine atoms, during the molecular fragmentation

Optically distinguishable electronic spin isomers of a stable organic diradical

Herein, we demonstrate a model of electronic spin isomers, the electronic counterpart of nuclear spin isomers, by employing a through-space conjugated stable organic diradical. We investigated a benzotriazinyl radical dimer linked via triptycene skeleton. The diradical has a small singlet–triplet energy gap of -3.0 kJ/mol, indicating ca. 1:1 coexistence of the two spin states at room temperature. The diradical at room temperature shows characteristic near-IR absorption bands around 500–900 nm, which is absent for the corresponding mono-radical subunit. Variable temperature measurement revealed that the absorbance of the NIR band depends on the abundance of the singlet state, and we assigned the NIR band as the singlet-specific absorption band. It enables photoexciting one of the two spin states coexisting in thermal equilibrium. Ultrafast transient spectroscopy disclosed that the two spin-states independently follow qualitatively different excited-state dynamics. Namely, the singlet excited state undergoes intramolecular symmetry-breaking charge transfer, and the triplet excited state goes exciton fusion to form a monomer-like excited state. These results demonstrate optically distinguishable spin isomers

Direct observation of photoionization dynamics in solution phase induced by femtosecond two-photon excitation

In solution phase, the solute can be photo-ionized in the lower excitation energy than its ionization potential in gas phase. Therefore, the specific interaction is expected to be exist between the surrounding media and higher excited (Sn) state of the solute. In order to elucidate such polarization effect of solvent on the photoionization process, femtosecond double-pulse excitation was applied to direct detection of low-energy photoionization dynamics of a phenylenediamine derivative in solution phase. From the results of the transient absorption change, in polar solvent, it is clearly indicated that photoionization does not proceed directly from the Sn state, but through specific intermediate state. Moreover

Optically Distinguishable Electronic Spin-isomers of a Stable Organic Diradical

電子のスピンに基づく新しい「異性体」を提唱 --スピン状態を色で見分けられる分子を創製--.京都大学プレスリリース. 2024-04-25.Herein, we introduce a model of electronic spin isomers, the electronic counterpart of nuclear spin isomers, by using a stable organic diradical. The diradical, composed of two benzotriazinyl radicals connected by a rigid triptycene skeleton, exhibits a small singlet–triplet energy gap of −3.0 kJ/mol, indicating ca. 1:1 coexistence of the two spin states at room temperature. The diradical shows characteristic near-IR absorption bands, which are absent in the corresponding monoradical subunit. Variable temperature measurements revealed that the absorbance of the NIR band depends on the abundance of the singlet state, allowing us to identify the NIR band as the singlet-specific absorption band. It enables photoexcitation of one of the two spin states coexisting in thermal equilibrium. Transient absorption spectroscopy disclosed that the two spin states independently follow qualitatively different excited-state dynamics. These results demonstrate a novel approach to the design and study of electronic spin isomers based on organic diradicals

Direct observation of photoionization dynamics in solution phase induced by femtosecond two-photon excitation

In solution phase, the solute can be photo-ionized in the lower excitation energy than its ionization potential in gas phase. Therefore, the specific interaction is expected to be exist between the surrounding media and higher excited (Sn) state of the solute. In order to elucidate such polarization effect of solvent on the photoionization process, femtosecond double-pulse excitation was applied to direct detection of low-energy photoionization dynamics of a phenylenediamine derivative in solution phase. From the results of the transient absorption change, in polar solvent, it is clearly indicated that photoionization does not proceed directly from the Sn state, but through specific intermediate state. Moreover