Propeller-Shaped Blatter-Based Triradicals: Distortion-Free Triangular Spin System and Spin-State-Dependent Photophysical Properties.

Herein, we report the synthesis and properties of triptycene-based C- and C-symmetric stable triradicals. SQUID magnetometry showed the propeller-shaped triradicals were both an antiferromagnetic equilateral triangle spin system with small spin-spin interactions J/k~-120 K and -106 K, leading to ca. 4/6 coexistence of the doublet/quartet states in thermal equilibrium at room temperature.

Excited State Dynamics of Geometrical Evolution of α-Substituted Dibenzoylmethanatoboron Difluoride Complex with Aggregation-Induced Emission Property.

Organic molecules with an aggregation-induced emission (AIE) property have been attracting much attention from the viewpoint of application to solid state emissive materials. For the AIE mechanism, quantum mechanical studies proposed the restriction of the intramolecular motion (RIM) model with the contribution of the conical intersection (CI) and deduced the importance of the restricted access to a conical intersection (RACI) in the potential energy surface (PES). Although these theoretical studies have contributed to the elucidation of AIE phenomena, direct detection of the reaction dynamics is indispensable to clarify the actual PES and the deactivation mechanism.

Molecular models of PM6 for non-fullerene acceptor organic solar cells: How DAD and ADA structures impact charge separation and charge recombination.

The quadrupole moment of a non-fullerene acceptor (NFA) generated by the constituent electron donor (D) and acceptor (A) units is a significant factor that affects the charge separation (CS) and charge recombination (CR) processes in organic photovoltaics (OPVs). However, its impact on p-type polymer domains remains unclear. In this study, we synthesized p-type molecules, namely acceptor-donor-acceptor (ADA) and donor-acceptor-donor (DAD), which are components of the benchmark PM6 polymer (D: benzodithiophene and A: dioxobenzodithiophene).

Spatially selective actuation of liquid-crystalline polymer films through two-photon absorption processes.

Soft materials that respond to external stimuli are promising candidates for next-generation actuators with human-friendly nature. Among various stimuli to induce strain, light offers spatial selectivity, which allows versatile motion of a continuous body. However, spatial selectivity of photoactuation has been limited in two dimension due to the predominant absorption of photons by chromophores near a light source in accordance with Beer-Lambert law.

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.

Visible-light-induced direct C-H alkylation of polycyclic aromatic hydrocarbons with alkylsulfones.

Polycyclic aromatic hydrocarbons (PAHs) are fragments of graphene that have attracted considerable attention as a new class of carbon-based materials. The functionalization of edge positions in PAHs is important to enable the modulation of physical and chemical properties essential for various applications. However, straightforward methods that combine functional group tolerance and regioselectivity remain sought after.

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

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.

Optically Distinguishable Electronic Spin-isomers of a Stable Organic Diradical.

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.

Site-Selective Photo-Crosslinking of Stilbene Pairs in a DNA Duplex Mediated by Ruthenium Photocatalyst.

We herein report a method for site-selective photo-crosslinking of a DNA duplex. A stilbene pair was introduced into a DNA duplex and a ruthenium complex was conjugated with a triplex-forming oligonucleotide. We demonstrated that [2+2] photocycloaddition of the stilbene pair occurred upon irradiation with visible light when the ruthenium complex was in close proximity due to triplex formation.

Impact of Ring-Closing on the Photophysical Properties of One-Dimensional π-Conjugated Molecular Aggregate.

The self-assembled state of molecules plays a pivotal role in determining how inherent molecular properties transform and give rise to supramolecular functionalities and has long attracted attention. However, understanding the influence of morphologies spanning the nano- to mesoscopic scales of supramolecular assemblies derived from identical intermolecular interactions has been notoriously challenging due to dynamic structural change and monomer exchange of assemblies in solution. In this study, we demonstrate that curved one-dimensional molecular assemblies (supramolecular polymers) of lengths of around 70-200 nm, originating from the same luminescent molecule, exhibit distinct photoluminescent properties when they form closed circular structures (toroids) versus when they possess chain termini in solution (random coils).

Gaining control on optical force by the stimulated-emission resonance effect.

The resonance between an electronic transition of a micro/nanoscale object and an incident photon flux can modify the radiation force exerted on that object, especially at an interface. It has been theoretically proposed that a non-linear stimulated emission process can also induce an optical force, however its direction will be opposite to conventional photon scattering/absorption processes. In this work, we experimentally and theoretically demonstrate that a stimulated emission process can induce a repulsive pulling optical force on a single trapped dye-doped particle.

Photoinduced crystal melting with luminescence evolution based on conformational isomerisation.

The phenomenon of crystal melting by light irradiation, known as photo-induced crystal-to-liquid transition (PCLT), can dramatically change material properties with high spatiotemporal resolution. However, the diversity of compounds exhibiting PCLT is severely limited, which hampers further functionalisation of PCLT-active materials and the fundamental understandings of PCLT. Here, we report on heteroaromatic 1,2-diketones as the new class of PCLT-active compounds, whose PCLT is based on conformational isomerisation.

A Kinetically Stabilized Nitrogen-Doped Triangulene Cation: Stable and NIR Fluorescent Diradical Cation with Triplet Ground State.

A kinetically-stabilized nitrogen-doped triangulene cation derivative has been synthesized and isolated as the stable diradical with a triplet ground state that exhibits near-infrared emission. As was the case for a triangulene derivative we previously synthesized, the triplet ground state with a large singlet-triplet energy gap was experimentally confirmed by magnetic measurements. In contrast to the triangulene derivative, the nitrogen-doped triangulene cation derivative is highly stable even in solution under air and exhibits near-infrared absorption and emission because the alternancy symmetry of triangulene is broken by the nitrogen cation.

Cage-Like Sodalite-Type Porous Organic Salts Enabling Luminescent Molecule's Incorporation and Room-temperature Phosphorescence Induction in Air.

Expression of room-temperature phosphorescence (RTP) in organic materials requires complicated molecular design and specific intermolecular interactions, and therefore types of RTP materials are restricted. This work presents cage-like sodalite-type porous organic salts (s-POSs) as host materials for luminescent molecules to induce RTP, using tetrasulfonic acid with an adamantane core and triphenylmethylamines that are modified with substituents in the para-positions of benzene rings (TPMA-X). By adding a representative luminescent molecule (pyrene) to a reaction solution during construction of s-POSs, the molecule is incorporated in a facile manner.

-Indacene Revisited: Modular Synthesis and Modulation of Structures and Molecular Orbitals of Hexaaryl Derivatives.

Though -indacene is an intriguing antiaromatic hydrocarbon of 12 π-electrons, it has been underrepresented due to the lack of efficient and versatile methods to prepare stable derivatives. Herein we report a concise and modular synthetic method for hexaaryl--indacene derivatives bearing electron-donating/-accepting groups at specific positions to furnish -, -, and -symmetric substitution patterns. We also report the effects of substituents on their molecular structures, frontier molecular orbital (MO) levels, and magnetically induced ring current tropicities.

Impact of Hydrophobic/Hydrophilic Balance on Aggregation Pathways, Morphologies, and Excited-State Dynamics of Amphiphilic Diketopyrrolopyrrole Dyes in Aqueous Media.

We report the thermodynamic and kinetic aqueous self-assembly of a series of amide-functionalized dithienyldiketopyrrolopyrroles (TDPPs) that bear various hydrophilic oligoethylene glycol (OEG) and hydrophobic alkyl chains. Spectroscopic and microscopic studies showed that the TDPP-based amphiphiles with an octyl group form sheet-like aggregates with J-type exciton coupling. The effect of the alkyl chains on the aggregated structure and the internal molecular orientation was examined via computational studies combining MD simulations and TD-DFT calculations.

Edge-to-Center Propagation of Photochemical Reaction during Single-Crystal-to-Single-Crystal Photomechanical Transformation of 2,5-Distyrylpyrazine Crystals.

Photomechanical molecular crystals are promising materials for photon-powered artificial actuators. To interpret the photomechanical responses, the spatiotemporal distribution of photoproducts in crystals could be an important role in addition to molecular structures, molecular packings, illumination conditions, crystal morphology, crystal size, and so on. In this study, we have found that single crystals of 2,5-distyrylpyrazine show a smooth single-crystal-to-single-crystal photomechanical expansion, and the photochemical reaction propagates from the edge to the center of the single crystal.

All-Visible (>500 nm)-Light-Induced Diarylethene Photochromism Based on Multiplicity Conversion via Intramolecular Energy Transfer.

Photoswitching molecules that reversibly switch upon visible-light irradiation are some of the most attractive targets for biological and imaging applications. In this study, we found a diarylethene (DAE) derivative having a covalently attached perylenebisimide (PBI) unit (DAE-PBI dyad) underwent an unexpected cyclization reaction upon irradiation with green (500-550 nm) light, where the DAE unit has no absorbance. The photoreactivity was enhanced in solvents containing heavy atoms and in the presence of oxygen.

Femtosecond dynamics of stepwise two-photon ionization in solutions as revealed by pump-repump-probe detection with a burst mode of photoexcitation.

Pump-repump-probe spectroscopy with a burst mode of photoexcitation was applied to the direct observation of the photoionization dynamics of perylene in the solution phase. Irradiation of a pump pulse train generated with birefringent crystals effectively accumulated an intermediate S state and a repump pulse triggered photoionization in the higher excited state, ensuring sufficiently large signal intensity to probe. Two-photon excitation to the energy level, which is 0.

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.

Fluorescent supramolecular polymers of barbiturate dyes with thiophene-cored twisted π-systems.

Because supramolecular polymerization of emissive π-conjugated molecules depends strongly on π-π stacking interaction, the formation of well-defined one-dimensional nanostructures often results in a decrease or only a small increase of emission efficiency. This is also true for our barbiturate-based supramolecular polymers wherein hydrogen-bonded rosettes of barbiturates stack quasi-one-dimensionally through π-π stacking interaction. Herein we report supramolecular polymerization-induced emission of two regioisomeric 2,3-diphenylthiophene derivatives functionalized with barbituric acid and tri(dodecyloxy)benzyl wedge units.

1,2,3-Tri(9-anthryl)benzene: Photophysical Properties and Solid-State Intermolecular Interactions of Radially Arranged, Congested Aromatic π-Planes.

We report the Negishi coupling based synthesis of 1,2,3-tri(9-anthryl)benzene derivatives containing three radially arranged anthracenes in a π-cluster. In the crystalline state of the unsubstituted derivative, intermolecular π-π and CH-π interactions between the anthracene units drive the formation of the two-dimensional packing structure. Owing to though-space π-conjugation between anthracene units, the substances have unique electronic properties.

Molecular crystalline capsules that release their contents by light.

Here, we present single crystalline capsules of a photoresponsive molecule produced by simple recrystallization from organic solutions without direct human processing. During the crystal growth process, a movie was taken of the capsule taking in the organic solution. The capsules responded rapidly (<1 s) to the UV light stimuli and released the captured solution or solute.

Direct determination of molar absorption coefficients of several molecules in the lowest excited singlet states.

Molar absorption coefficient of the lowest excited state is an indispensable information for the quantitative investigation of photochemical reactions by means of transient absorption spectroscopy. In the present work, we quantitatively estimated the molar absorption coefficients of the S state of the solute in three solution systems, Rhodamine B in ethanol, ZnTPP in DMF and N,N'-bis(2,6-diisopropylphenyl)terrylene-3,4,11,12-tetracarboxydiimide (TDI) in chloroform, by perfectly bleaching the ground state molecules using the picosecond 532-nm laser pulse with a large number of photons. These solution systems were selected because no obvious photodegradation was detected in the present range of the excitation intensity.

Slow photoionization via higher excited states of N,N-dimethylaniline in ethanol solution probed by femtosecond transient absorption spectroscopy under two-pulse two-photon excitation.

Photoionization dynamics of N,N-dimethylaniline (DMA) from highly electronically excited states in ethanol solution was investigated by means of femtosecond two-pulse two-photon excitation transient absorption (2PE-TA) spectroscopy. The first pump pulse prepares the lowest singlet excited state (S state) of DMA, and the second one excites the S state into higher excited states. In the case with the second pulse at 500 nm, the ionization took place via a rapid channel (<100 fs) and a slow one with the time constant of ∼10 ps.