A Hexaarylbiimidazole-Terarylene Hybrid: Visible-to-NIR-II Absorption via Sequential Photochromic Reactions.

A synergetic interaction between two or more photochromic chromophores has a potential to achieve advanced photochemical properties beyond conventional photochromic molecules and to realize photochemical control of complex systems using only a single molecule. Herein, we report a hybrid photochromic molecule consisting of hexaarylbiimidazole (HABI) and terarylene that exhibits multi-state photochromism. The biphotochrome hybrid shows four-state photochromic reaction involving sequentially proceeding photoreactions. The UV or visible light irradiation to the biphotochrome leads to the C-N bond breaking reaction of the HABI in preference to the ring-closing reaction of the 6π-electron system in the terarylene unit, leading to two terarylene radical molecules. The photogenerated terarylene radical further exhibits the 6π-electrocyclization reaction by UV irradiation. The delocalized π-radical on the closed-ring form of the terarylene is efficient to enhance the photosensitivity to the NIR-I and -II region. Furthermore, a recombination reaction of radicals between the open- and closed-ring isomers of terarylene affords an unprecedented photochromic dimer as a structural isomer of the initial molecule. This is a consequence of the sequential hybrid photochromic system involving the HABI and terarylene units.

Bridged-Imidazole Dimer Exhibiting Three-State Negative Photochromism with a Single Photochromic Unit.

Photochromic molecules that can exhibit multiple states of photochromism in a single photochromic unit are considered more attractive than traditional bistable photochromic molecules because they can offer more versatility and control in photoresponsive systems. We have synthesized a negative photochromic 1-(1-naphthyl)pyrenyl-bridged imidazole dimer (NPy-ImD) that has three different isomers: a colorless isomer, 6MR, a blue-colored isomer, 5MR-B, and a red-colored isomer, 5MR-R. NPy-ImD can interconvert between these isomers via a short-lived transient biradical, BR, upon photoirradiation. 5MR-R is the most stable isomer, and the energy levels of 6MR, 5MR-B, and BR are relatively close to each other. The colored isomers 5MR-R and 5MR-B are photochemically isomerized to 6MR via the short-lived BR upon irradiation with blue light and red light, respectively. The absorption bands of 5MR-R and 5MR-B are well separated by more than 150 nm, with a small overlap, which means they can be selectively excited with different light sources, visible light for 5MR-R and NIR light for 5MR-B. The colorless isomer 6MR is formed from the short-lived BR through a kinetically controlled reaction. 6MR and 5MR-B can then be converted to the more stable isomer 5MR-R through a thermodynamically controlled reaction, which is facilitated by the thermally accessible intermediate, BR. Notably, 5MR-R photoisomerizes to 6MR when irradiated with CW-UV light, whereas it photoisomerizes to 5MR-B by a two-photon process when irradiated with nanosecond UV laser pulses.

Controlling Diradical Character of Photogenerated Colored Isomers of Phenoxyl-Imidazolyl Radical Complexes.

We propose a rational method for evaluating the diradical character of the photochromic phenoxyl-imidazolyl radical complex (PIC) derivatives based on their radical-radical coupling reaction rates. PIC consists of an imidazole ring, a phenoxyl ring, and a bridging unit that structurally connects them. The C-N bond formed between the imidazole and phenoxyl rings can be dissociated photochemically in a homolytic manner. The photochromism of PIC differs significantly from other photochromic molecules in that the transient colored open-ring isomer has a diradical character. The colored open-ring isomer returns promptly to the initial colorless closed-ring isomer by the intramolecular radical recombination reaction. By changing the aromaticity and substitution position of the bridging unit, it is possible to control the degree of contribution of the open-shell diradical and closed-shell quinoidal structures to the open-ring isomer. Systematic investigation of the photochromic reactions of several PIC derivatives revealed that the half-life of the open-ring isomers reflects the diradical character. Thus, the radical recombination reaction rate of the open-ring isomer of the PIC derivatives is an excellent parameter of the diradical character.

Excitation wavelength- and intensity-dependent stepwise two-photon-induced photochromic reaction.

The photochromic molecules showing wavelength-selective or light intensity-dependent photoresponse are receiving increased attention in recent years. Although a photoswitch with a single chromophore can control the ON and OFF states of a function, that consisting of multi-chromophores would be useful for the specific control in complex systems. Herein, we designed stepwise two-photon induced photochromic molecules (PABI-PIC and PABI-PIC2) consisting of two different photochromic units (PABI and PIC). One-photon absorption reaction in the UV light region of PABI-PIC generates the short-lived transient biradical (BR) that absorbs an additional photon in the visible and UV light region in a stepwise manner to produce the two-photon photochemical product, the quinoidal species (Quinoid). The photochromic properties of these transient species are completely different in color and fading speed. In addition, PABI-PIC also shows the excitation wavelength-dependent photochromism because the excited states of the PABI and PIC units are electronically orthogonal. Therefore, the stepwise photochromic properties of PABI-PIC are easily controlled depending on the excitation light intensity and wavelength. These molecular designs are important for the development of advanced photoresponsive materials.

Dynamic Spin-Spin Interaction Observed as Interconversion of Chemical Bonds in Stepwise Two-Photon Induced Photochromic Reaction.

Biradicaloids in π-conjugated organic molecules have been extensively studied in recent years because of the fundamental insights into the chemical bonds and unique optical, electrical, and magnetic properties. Several studies have reported that the spin-spin interactions of biradicaloids with flexible molecular frameworks dynamically evolve correlating with molecular structural changes. Although these dynamic behaviors will provide important insights into the relationship between molecular structures and spin properties, studies on such behaviors have been limited to two-spin systems. Here, we investigated the stepwise photochromic properties of biphotochromic molecules involving multiple spin interactions by double-pulse laser flash photolysis. The one-photon photochromic reaction generates the o-biradical form as the open-closed form, which thermally isomerizes to the o-quinoidal form and reaches the thermal equilibrium state between them. The additional absorption of a photon by the open-closed form leads to the photochromic reaction of the other photochromic unit, resulting in the generation of unpaired spins at the p-position of the central aromatic bridge of the biradical or quinoidal form. Under the situation, while the interaction between the unpaired spins and the o-biradical preferentially produces the p-quinoidal form in which the antiferromagnetic interaction at the p-position is dominant, that between the spins and the o-quinoidal form kinetically produces the bis(o-quinoidal) form followed by the thermal isomerization to the thermodynamically stable p-quinoidal form. These dynamic spin-spin interactions along with the rearrangement of chemical bonds will give a deeper understanding of the singlet biradicaloids and that to bridge organic multiradicals in molecular systems to cooperative spin behaviors in bulk materials.

Red or Near-Infrared Light Operating Negative Photochromism of a Binaphthyl-Bridged Imidazole Dimer.

The development of red or near-infrared light (NIR) switchable photochromic molecules is required for an efficient utilization of sunlight and regulation of biological activities. While the photosensitization of photochromic molecules to red or NIR light has been achieved by a two-photon absorption process, the development of a molecule itself having sensitivity to red or NIR light has been now a challenging study. Herein, we developed an efficient molecular design for realizing red or NIR-light-responsive negative photochromism based on binaphthyl-bridged imidazole dimers. The introduction of electron-donating substituents shows the red shift of the absorption band at the visible-light region because of the contribution of a charge-transfer transition. Especially, the introduction of a di(4-methoxyphenyl)amino group (TPAOMe) and a perylenyl group largely shifts the absorption edge of the stable colored form to 900 nm. In addition, because the absorption band of one of the derivatives substituted with TPAOMe covers the whole visible-light region, the colored form shows a neutral gray color. Upon red (660 nm) or NIR-light (790 nm) irradiation, we observed the negative photochromic reaction from the stable colored form to the metastable colorless form. Therefore, the substituted binaphthyl-bridged imidazole dimers constitute the attractive photoswitches within a biological window.

Photochromic Radical Complexes That Show Heterolytic Bond Dissociation.

Photochromic materials have been widely used in various research fields because of their variety of photoswitching properties based on various molecular frameworks and bond breaking processes, such as homolysis and heterolysis. However, while a number of photochromic molecular frameworks have been reported so far, there are few reports on photochromic molecular frameworks that show both homolysis and heterolysis depending on the substituents with high durability. The biradicals and zwitterions generated by homolysis and heterolysis have different physical and chemical properties and different potential applications. Therefore, the rational photochromic molecular design to control the bond dissociation in the excited state on demand expands the versatility for photoswitch materials beyond the conventional photochromic molecular frameworks. In this study, we synthesized novel photochromic molecules based on the framework of a radical-dissociation-type photochromic molecule: phenoxyl-imidazolyl radical complex (PIC). While the conventional PIC shows the photoinduced homolysis, the substitution of a strong electron-donating moiety to the phenoxyl moiety enables the bond dissociation process to be switched from homolysis to heterolysis. This study gives a strategy for controlling the bond dissociation process of the excited state of photochromic systems, and the strategy enables us to develop further novel radical and zwitterionic photoswitches.

Enhancement of Negative Photochromic Properties of Naphthalene-Bridged Phenoxyl-Imidazolyl Radical Complex.

Negative photochromism has increased attention as a light-switch for functional materials. A development of fast photochromic molecules has been also expected because a rapid thermal back reaction within a millisecond time scale is useful for real-time switching. Herein, we synthesized the derivatives of the naphthalene-bridged phenoxyl-imidazolyl radical complex (Np-PIC) showing the negative photochromism to demonstrate the efficient strategy to increase the visible light sensitivity and to control the thermal back reaction rates. The distances of the C-C bond of the transient 2,4'-isomer shows good agreement with the thermodynamic stability, leading to the control of the thermal back reaction rate. We revealed the cyclic voltammetry and the DFT calculations are efficient to predict the characters of the HOMO and LUMO. The introduction of the electron-withdrawing dicyanoquinodimethane group is efficient to induce the photochromic reaction with increased visible-light sensitivity by the expansion of the π-conjugation. The results will give an important insight for the future development of fast-responsive negative photochromic molecules.

Turn-On Mode Fluorescence Switch by Using Negative Photochromic Imidazole Dimer.

The development of fluorescence switchable molecules in several polar and apolar environments has been required for fluorescence imaging of nanostructures. Photochromic molecules are an important class for the reversible light-triggered fluorescence switching. Although many studies of fluorescence switching by using photochromic reactions have been reported, the report of photochromic molecules reversibly showing turn-on mode fluorescence switching has been limited in spite of their importance. Herein, we report the photoactivatable fluorescence based on negative photochromism, where the absorption spectrum of the compound after irradiation is blue-shifted relative to that before irradiation. We introduced naphthalimide units as a green fluorophore to the negative photochromic binaphthyl-bridged imidazole dimer. The fluorescence of the naphthalimide unit is efficiently quenched in the initial colored isomer (fluorescence quantum yield: Φfluo. = 0.01) by Förster resonance energy transfer. In contrast, the fluorescence quantum yield increases up to 0.75 in the transient isomer formed by the negative photochromic reaction. The fluorescence intensity thermally decreases with the thermal back reaction to form the original stable colored form. These results indicate that the negative photochromic molecules are suitable for turn-on mode fluorescence switches and will give an attractive insight for the development of reversible fluorescence switching molecules.

Photochromic Reaction by Red Light via Triplet Fusion Upconversion.

Red or near-infrared (NIR) light responsive molecules have received much attention for biological and material applications because potentially harmful UV light for materials and cells is not required for the photochemical reactions. Although some molecular designs for photochromic molecules to increase the photosensitivity to red or NIR light have been reported, the strategies are limited to the extension of π-conjugation length and the utilization of charge transfer transition or energy and electron transfers. Triplet fusion is an attractive tool to cause chemical reactions by converting low-energy excitation light to high-energy upconversion light. However, the efficient use of the high energy of upconversion light is difficult because almost all reported triplet fusion systems rely on reabsorption of upconversion light. Here, we demonstrated red-light-driven photochromism via the triplet fusion of a phenoxyl-imidazolyl radical complex, Pery-RPIC, that has a covalently bonded perylene as an annihilator unit. The femtosecond time-resolved absorption and fluorescence spectroscopy revealed that this photochromic reaction proceeds by the highly efficient singlet energy transfer from the annihilator unit to the photochromic unit. This strategy can be applied not only to the development of visible and NIR light responsive photochromic system but also to various photochemical reactions.

Photo- and Electro-Driven Molecular Switching System of Aryl-Bridged Photochromic Radical Complexes.

Fast photochromic molecules have received much interest in the potential application as a real-time switching trigger in material and biological chemistry. Pentaarylbiimidazole (PABI) and phenoxyl-imidazolyl radical complex (PIC) are one of the fast photochromic molecules based on imidazolyl radicals. Because the photochromic reaction of these fast photochromic molecules proceeds from the optically forbidden S1 state, it is difficult to estimate the excitation energy to induce the photochromic reactions by spectroscopic techniques. In this study, we performed the electrochemical measurements for PABI and PIC to investigate the electronic properties and to determine the S0-S1 transition energies. In addition, we also revealed that the electrochemical reduction of PABI and PIC generates the radical anion which spontaneously shows the C-N bond breaking reaction to produce the radical species. The initial photochromic dimer is reproduced by the reversible oxidation of the anion species. This characteristic photochromic and electrochromic properties can be applicable to the photowritable electrochromic devices with high spatial resolution.

Excited state dynamics for visible-light sensitization of a photochromic benzil-subsituted phenoxyl-imidazolyl radical.

Visible-light sensitized photoswitches have been paid particular attention in the fields of life sciences and materials science because long-wavelength light reduces photodegradation, transmits deep inside of matters, and achieves the selective excitation in condensed systems. Among various photoswitch molecules, the phenoxyl-imidazolyl radical complex (PIC) is a recently developed thermally reversible photochromic molecule whose thermal back reaction can be tuned from tens of nanoseconds to tens of seconds by rational design of the molecular structure. While the wide range of tunability of the switching speed of PIC opened up various potential applications, no photosensitivity to visible light limits its applications. In this study, we synthesized a visible-light sensitized PIC derivative conjugated with a benzil unit. Femtosecond transient absorption spectroscopy revealed that the benzil unit acts as a singlet photosensitizer for PIC by the Dexter-type energy transfer. Visible-light sensitized photochromic reactions of PIC are important for expanding the versatility of potential applications to life sciences and materials science.

Intensity-Dependent Photoresponse of Biphotochromic Molecule Composed of a Negative and a Positive Photochromic Unit.

Light-selective multiple photochromic systems are important for advanced photoswitching of chemical reactions and biological activities. While UV light has been frequently utilized to induce photochromic reactions, visible light is energetically acceptable to avoid undesired reactions. However, many of the reported multiphotochromic systems still rely on UV light to induce at least a part of photochromic reactions. In this work, we designed a biphotochromic molecule showing intensity-dependent multiple coloration with a visible-light source by incorporating two T-type photochromic units; a colorless positive photochromophore and a colored negative photochromophore in a molecule. The negative photochromophore acts as a visible-light sensitizer for the positive photochromic reaction. The compound shows an intensity-dependent color change under visible-light irradiation. The weak visible-light excitation leads to gradual decoloration from orange to yellow, whereas intense laser excitation clearly changes the color to green. This characteristic photochromism can be achieved by control of the photochromic reaction rates of the negative and positive photochromic reactions. The combination of negative and positive photochromic reactions gives attractive important insight into the development of multiresponsive optical materials.

Stepwise photochromism of bisnaphthopyrans exhibiting an excitation intensity-dependent color change.

Non-linear photoresponses against excitation light intensity are important for the development of attractive photofunctional materials exhibiting high spatial selective photoswitching that is not affected by weak background light. Biphotochromic systems composed of two fast photochromic units have the potential to show a stepwise two-photon absorption process in which the optical properties can be non-linearly controlled by changing the excitation light conditions. Herein, we designed and synthesized novel bisnaphthopyran derivatives containing fast photoswitchable naphthopyran units. The bisnaphthopyran derivatives show a stepwise two-photon-induced photochromic reaction upon UV light irradiation accompanied by a drastic color change due to a large change in the molecular structure between the one-photon product and the two-photon product. Consequently, the color of the bisnaphthopyran derivatives can be non-linearly controlled by changing the excitation intensity. This characteristic photochromic property of the biphotochromic system provides important insight into advanced photoresponsive materials.

Structurally and electronically modulated spin interaction of transient biradicals in two photon-gated stepwise photochromism.

The development of two-photon induced photochromic compounds is important for advanced photoresponsive materials. The utilization of the long-lived transient states or species for two-photon absorption is one of the efficient strategies to realize the advanced photochemical behavior beyond a one-photon photochemical reaction. We have synthesized bi-photochromic compounds composed of two photochromic phenoxyl-imidazolyl radical complex units. The biphotochromic compounds generate two biradical units when the two photochromic units absorb photons with a stepwise manner. The interaction between the two biradicals through the central bridging phenyl ring is the key feature to control the stepwise photochromic reaction. Here, we introduced aromatic spacers in order to modulate the distance and the dihedral angle between the biradical units. The color and the rate of the thermal back reaction of the stepwise photochromism can be regulated by the control of the central bridging part. These results give important insights to develop desirable advanced photoresponsive compounds.

Rate-Tunable Stepwise Two-Photon-Gated Photoresponsive Systems Employing a Synergetic Interaction between Transient Biradical Units.

The cooperative interaction between photons and molecules, recently termed as the "photosynergetic" effect, is crucial to develop advanced photofunctional materials beyond a one-photon reaction of a single chromophore. The two-photon absorption is one of the attractive processes for the efficient utilization of photons. Especially, the nonlinear response of the two-photon absorption process is of interest not only to realize temporal and spatial control of reactions but also to develop the rewritable optical memory media and smart optical devices responding to the intensity of light. The stepwise two-photon-induced photochromism, which involves a short-lived transient species as an intermediate state, is one of the advanced photoresponsive compounds. The key feature of the stepwise two-photon-induced photochromism is an effective electronic interaction between the photogenerated transient chromophores. Here, we designed bis(phenoxyl-imidazolyl radical complex) (bisPIC) derivatives, which are composed of a couple of photochromic units and absorb two photons in a stepwise manner. The stepwise photochromic properties were investigated in detail by using double pulse laser flash photolysis and time-resolved Fourier transform infrared (TR-FTIR) spectroscopy. The one-photon reaction leads to the generation of a short-lived biradical species, which absorbs an additional photon and generates two electronically coupled biradical units, resulting in the formation of the long-lived quinoid species. The short-lived biradical species and the long-lived quinoid species of each bisPIC derivatives show the significantly different absorption spectra and rates of the thermal back reactions. These results indicate the colors and the lifetimes of the transient species can be systematically changed by switching the wavelength and intensity of the excitation light. The development of an excitation light threshold system based on the fast-switchable photochromic compounds will give important insights not only for the development of functional photoresponsive materials but also for the fundamental research using the cooperative excitation and interaction between photochromophores.

A Simple and Versatile Strategy for Rapid Color Fading and Intense Coloration of Photochromic Naphthopyran Families.

Benzo-annulated chromenes, i.e., naphthopyrans, are well-known photochromic molecules that undergo photochemical ring-opening reactions to form two colored open-ring isomers, the transoid-cis and transoid-trans forms, upon light irradiation. Though the transoid-cis form returns thermally to the uncolored closed form, the fading rate of the transoid-trans form is extremely slow because of its higher thermal stability. This slow fading behavior of the transoid-trans form is responsible for the persistence of residual color for several minutes to hours, and prevents the application of such molecules to fast photoswitching materials. We have found a new simple and versatile strategy to substantially reduce the amount of the undesirable long-lived colored transoid-trans form by introducing an alkoxy group at the 1-position of azino-fused chromenes, i.e., 8H-pyranoquinazolines. The alkoxy group effectively reduces the formation of the transoid-trans form due to C-H···O intramolecular hydrogen bonding in the transoid-cis form. Moreover, the introduction of a condensed aromatic ring at the 3-position was found to be effective to increase the photosensitivity of the ring-opening reaction. This strategy can also be applied for naphthopyran derivatives and is useful for the development of fast photoresponsive photochromic lenses and fast photoswitching applications such as dynamic holographic materials and molecular actuators.

Direct Observation of the Ultrafast Evolution of Open-Shell Biradical in Photochromic Radical Dimer.

Delocalized biradicals have been extensively studied because of fundamental interests to singlet biradicals and several potential applications such as to two-photon absorption materials. However, many of the biradical studies only focus on the static properties of the rigid molecular structures. It is expected that the biradical properties of the delocalized biradicals are sensitive to the subtle changes of the molecular structures and their local environments. Therefore, the studies of the dynamic properties of the system will give further insight into stable radical chemistry. In this study, we directly probe the ultrafast dynamics of the delocalized biradical of a photochromic radical dimer, pentaarylbiimidazole (PABI), by time-resolved visible and infrared spectroscopies and quantum chemical calculations with the extended multistate complete active space second-order perturbation theory (XMS-CASPT2). While the photogenerated transient species was considered to be a single species of the biradical, the present ultrafast spectroscopic study revealed the existence of two transient isomers differing in the contributions of biradical character. The origin of the two metastable isomers is most probably due to the substantial van der Waals interaction between the phenyl rings substituted at the imidazole rings. Unraveling the temporal evolution of the biradical contribution will stimulate to explore novel delocalized biradicals and to develop biradical-based photofunctional materials utilizing the dynamic properties.

Stepwise Two-Photon-Gated Photochemical Reaction in Photochromic [2.2]Paracyclophane-Bridged Bis(imidazole dimer).

Stepwise two-photon processes not only have great potential for efficient light harvesting but also can provide valuable insights into novel photochemical sciences. Here we have designed a [2.2]paracyclophane-bridged bis(imidazole dimer), a molecule that is composed of two photochromic units and absorbs two photons in a stepwise manner. The absorption of the first photon leads to the formation of a short-lived biradical species (half-life = 88 ms at 298 K), while the absorption of the additional photon by the biradical species triggers a subsequent photochromic reaction to afford a long-lived quinoid species. The short-lived biradical species and the long-lived quinoid species display significantly different absorption spectra and rates of the thermal back-reaction. The stepwise two-photon excitation process in this photochromic system can be initiated even by incoherent continuous-wave light irradiation, indicating that this two-photon reaction is highly efficient. Our molecule based on the bridged bis(imidazole dimer) unit should be a good candidate for multiphoton-gated optical materials.

Self-Contained Photoacid Generator Triggered by Photocyclization of Triangle Terarylene Backbone.

We herein propose a new type of efficient neutral photoacid generator. A photoinduced 6π-electrocyclization reaction of photochromic triangle terarylenes triggers subsequent release of a Brønsted acid, which took place from the photocyclized form. A H-atom and its conjugate base were introduced at both sides of a 6π-system to form the self-contained photoacid generator. UV irradiation to the 6π-system produces a cyclohexa-1,3-diene part with a H-atom and a conjugate base on the sp(3) C-atoms at 5- and 6-positions, respectively, which spontaneously release an acid molecule quantitatively forming a polyaromatic compound. A net quantum yield of photoacid generation as high as 0.52 under ambient conditions and a photoinitiated cationic polymerization of an epoxy monomer are demonstrated.