Red-Light-Driven Bifunctionalization of Styrene Derivatives.

A red-light-activated phthalocyanine ruthenium complex has been designed as a catalyst for the bifunctionalization of styrene derivatives. The combination of a trifluoromethylation agent resistant to nucleophiles and various nucleophiles facilitates the concurrent incorporation of a trifluoromethyl group and various functional groups onto the double bond of the substrate. This reaction demonstrates the utility of mild, low-energy, and highly transmissive long-wavelength light for intricate molecular transformations in a one-pot procedure.

Selective Formation of Cu Active Sites with Different Coordination States on Pseudospinel CuAl2O4 and Their NO Reduction Catalysis.

In the spinel framework, copper (Cu) in two distinct coordination states exhibits catalytic activity for NO reduction through different mechanisms. However, detailed exploration of their respective catalytic properties, such as the redox behavior of Cu and substrate molecule adsorption, has been challenging due to difficulties in their separate formation. In this study, we present the controlled formation of pseudospinel CuAl2O4, containing exclusively tetrahedrally or octahedrally coordinated Cu, achieved by manipulating aging temperature and O2 concentration. Through these materials, we observed that in the CO-NO reaction, the step primarily determining the rate differs: NO reduction dominates with octahedrally coordinated Cu, whereas carbon monoxide (CO) oxidation is prominent with tetrahedrally coordinated Cu. The lower coordination number of Cu significantly benefits NO reduction but negatively impacts the CO-NO reaction, albeit positively influencing NO reduction in three-way catalytic reactions.

Dehydro[12]- and [18]annulene-Fused Ball-Shaped Ruthenium Complex Oligomers: Synthesis, Aromatic/Antiaromatic Effect, and Symmetry for Near-Infrared Optical Properties.

The appropriate arrangement of near-infrared (NIR) chromophores allows for the modification of the peak wavelength in the NIR region and efficient use of NIR light. However, the preparation of novel NIR chromophores using simple procedures remains a formidable challenge. Herein, we report the synthesis of ball-shaped ruthenium complex oligomers. The metal complexes can be synthesized in a single step and interact strongly with NIR light. Alkyne-substituted low-symmetry ball-shaped ruthenium complexes were synthesized and subjected to Eglinton coupling to obtain dehydro[12] and [18]annulene-fused dimers and trimers. Fine-tuning of the reaction conditions led to the selective synthesis of the target oligomers. NMR spectroscopy confirmed that the 18π-aromatic and 12π-antiaromatic properties of the annulene influenced the ruthenium complex chromophore, and magnetic circular dichroism spectroscopy showed changes in the electronic structure of their excited state owing to molecular-symmetry differences. The absorption coefficient in the NIR region of the absorption spectra of the oligomers increased significantly, supporting the efficient use of light by oligomerization. The formation of oligomers using ball-shaped metal complexes is a simple and effective strategy for controlling NIR optical properties.

Phosphorus(V) Tetraazaporphyrin with an Intense, Broad CT Band in the Near-IR Region.

In phosphorus tetraazaporphyrins (PTAPs), the Q- and charge-transfer (CT) bands appear as a result of configuration interaction between their excited states. On the basis of this concept, a PTAP with an intense, broad CT band in the near-IR region has been rationally designed and realized by introducing eight diphenylaminophenyl (dPAP) groups. The order of the CT and Q-bands in ascending energy was supported by magnetic circular dichroism (MCD) spectroscopy and theoretical calculations. An intense two-photon absorption was also found in the deep near-IR region.

Phototriggered Butenolide Formation from a Cyclobutenedione and an Acidic Nucleophile.

A phototriggered conjugation reaction of an aminocyclobutenedione and an acidic nucleophile was discovered. Upon blue light irradiation of the materials, a butenolide derivative with substituents derived from the aminocyclobutenedione and the nucleophile was produced. The reaction proceeded efficiently under organic solvent or organic solvent/aqueous buffer (1/1) conditions. This reaction would be useful for the synthesis of unique butenolide derivatives and derivatization of acidic functional groups contained in aqueous biomolecules.

Photosensitizing Metasurface Empowered by Enhanced Magnetic Field of Toroidal Dipole Resonance.

Photochemical reaction exploiting an excited triplet state (T1 ) of a molecule requires two steps for the excitation, i.e., electronic transition from the ground (S0 ) to singlet excited (S1 ) states and intersystem crossing to the T1  state. A dielectric metasurface coupled with photosensitizer that enables energy efficient photochemical reaction via the enhanced S0 →T1 magnetic dipole transition is developed. In the direct S0 →T1 transition, the photon energy of several hundreds of meV is saved compared to the conventional S0 → S1 →T1 transition. To maximize the magnetic field intensity on the surface, a silicon (Si) nanodisk array metasurface with toroidal dipole resonances is designed. The surface of the metasurface is functionalized with ruthenium (Ru(II)) complexes that work as a photosensitizer for singlet oxygen generation. In the coupled system, the rate of the direct S0 →T1 transition of Ru(II) complexes is 41-fold enhanced at the toroidal dipole resonance of a Si nanodisk array. The enhancement of a singlet oxygen generation rate is observed when the toroidal dipole resonance of a Si nanodisk array is matched with the direct S0 →T1 transition wavelength of Ru(II) complexes.

Cationic Axial Ligand Effects on Sulfur-Substituted Subphthalocyanines.

Herein, we report the synthesis of sulfur-substituted boron(III) subphthalocyanines (SubPcs) with cationic axial ligands. Subphthalocyanines were synthesized by a condensation reaction using the corresponding phthalonitriles and boron trichloride as a template. An aminoalkyl group was introduced on the central boron atom; this process was followed by N-methylation to introduce a cationic axial ligand. The peripheral sulfur groups shifted the Q band of SubPcs to a longer wavelength. The cationic axial ligands increased the polarity and enhanced the hydrophilicity of SubPcs. The effect of axial ligands on absorption and fluorescence properties is generally small. However, a further red shift was observed by introducing cationic axial ligands into the sulfur-substituted SubPcs. This change is similar to that in sulfur-substituted silicon(IV) phthalocyanines. The unique effect of the cationic axial ligand was extensively investigated by theoretical calculations and electrochemistry. In particular, the precise oxidation potential was determined using ionization potential measurements. Thus, the results of the present study provide a novel strategy for developing functional dyes and pigments based on SubPcs.

Direct Near Infrared Light-Activatable Phthalocyanine Catalysts.

The high penetration of near-infrared (NIR) light makes it effective for use in selective reactions under light-shielded conditions, such as in sealed reactors and deep tissues. Herein, we report the development of phthalocyanine catalysts directly activated by NIR light to transform small organic molecules. The desired photocatalytic properties were achieved in the phthalocyanines by introducing the appropriate peripheral substituents and central metal. These phthalocyanine photocatalysts promote cross-dehydrogenative-coupling (CDC) under irradiation with 810 nm NIR light. The choice of solvent is important, and a mixture of a reaction-accelerating (pyridine) and -decelerating (methanol) solvents was particularly effective. Moreover, we demonstrate photoreactions under visible-light-shielded conditions through the transmission of NIR light. A combined experimental and computational mechanistic analysis revealed that this NIR reaction does not involve a photoredox-type mechanism with electron transfer, but instead a singlet-oxygen-mediated mechanism with energy transfer.

Red-light-activatable ruthenium phthalocyanine catalysts.

Phthalocyanine ruthenium complexes were identified as red-light activatable catalysts for trifluoromethylation reactions. The red-light mediated chlorotrifluoromethylation of alkenes could proceed without any sacrificial reducing reagents. This reaction exhibited good compatibility with a blue-light-absorbing substrate, while under irradiation with blue light, i.e., under traditional photoreaction conditions, this substrate decomposed completely.

Direct Excitation of Triplet State of Molecule by Enhanced Magnetic Field of Dielectric Metasurfaces.

Efficient excitation of a triplet (T1 ) state of a molecule has far-reaching effects on photochemical reaction and energy conversion systems. Because the optical transition from a ground singlet (S0 ) to a T1 state is spin-forbidden, a T1 state is generated via intersystem crossing (ISC) from an excited singlet (S1 ) state. Although the excitation efficiency of a T1 state can be increased by enhancing ISC utilizing a heavy atom effect, energy loss during S1 →T1 relaxation is inevitable. Here, a general approach to directly excite a T1 state from a ground S0 state via magnetic dipole transition, which is boosted by enhanced magnetic field induced by a dielectric metasurface, is proposed. As a dielectric metasurface, a hexagonal array of silicon (Si) nanodisks is employed; the nanodisk array induces a strongly enhanced magnetic field on the surface due to the toroidal dipole (TD) resonance. A proof-of-concept experiment is performed using ruthenium (Ru) complexes placed on a metasurface and demonstrates that the phosphorescence is 35-fold enhanced on a metasurface when the TD resonance is tuned to the wavelength of the direct S0 →T1 transition. These results indicate that photon energy necessary to excite the T1 state can be reduced by more than 400 meV compared to the process involving the ISC. By combining optical measurements with numerical simulations, the mechanism of the phosphorescence enhancement is quantitatively discussed.

Fluorescent-Oxaboroles: Synthesis and Optical Property by Sugar Recognition.

The optical property of fluorescent unit-conjugated aliphatic oxaboroles has been investigated. The oxaboroles provide good fluorescence quantum yields and selective recognition toward D-ribose and D-ribose containing molecules. The molecular recognition induced significant fluorescence quenching. The property of the boroles showed the possibility of the boron-based nicotinamide adenine dinucleotide (NAD) sensor probe.

Synthesis and characterization of heteroleptic rare earth double-decker complexes involving tetradiazepinoporphyrazine and phthalocyanine macrocycles.

Reaction of (2,3,9,10,16,17,23,24-octabutylphthalocyaninato)lanthanide(iii) acetylacetonates (BuPcLn(acac), 1a-c, Ln = Lu (a), Eu (b), La (c)) with a tetrakis(5,7-bis(4-tert-butylphenyl)-6H-1,4-diazepino)[2,3-b,g,l,q]porphyrazine ligand (tBuPhDzPzH2, 2) produced sandwich compounds (tBuPhDzPz)Ln(BuPc) (3a-c), which represent the first heteroleptic double-deckers incorporating both Pc and DzPz decks. A combination of high-resolution mass spectrometry, UV-Vis/NIR, MCD, and 1H NMR spectroscopy, and square-wave voltammetry provided unambiguous characterization of target complexes 3 indicating that their spectral and electrochemical properties are generally intermediate with respect to their homoleptic relatives. Based on the data of solution-state 1H-1H NMR (COSY, NOESY) correlation spectroscopy supported by DFT calculations, a dimerization tendency of compounds 3 proportional to the Ln(iii) ion size was found. The spectroelectrochemical study of 3 and the corresponding homoleptic double-deckers revealed a pronounced tendency to aggregation of the one-electron oxidized forms of DzPz-containing double-decker complexes compared to homoleptic Pc2Ln compounds.

Efficiency Enhancement of a Photocatalytic Decarbonylation of an Aminocyclopropenone by Benzothiophene Substitution.

To improve the efficiency of the photocatalytic decarbonylation of cyclopropenones, the effects of substituents on cyclopropenone were explored. A benzothiophene-substituted aminocyclopropenone exhibited significantly improved decarbonylation efficiency to produce the corresponding ynamine, which worked as a potent dehydration condensation agent. The benzothiophene derivative was applicable to the photocatalytic reaction in the presence of potential excited-state quenchers such as oxygen and anilines. The high catalyst sensitivity would be attributed to the involvement of triplet energy transfer reaction pathway, which was not observed in the reaction with previously reported aminocyclopropenones.

Temperature-dependent changes in the molecular orientation and visible color of phthalocyanine films.

A simple phthalocyanine zinc complex exhibits a visible color change in response to weak external stimuli, i.e., changes in solvent and temperature. Its chromism was attributed to its controlled aggregation via weak interactions between the central metal and peripheral oxygen atoms. In solution, intense absorption and fluorescence bands appeared in both the longer-wavelength and NIR region in non-coordinating solvents, while a simple sharp Q band was observed in coordinating solvents. Variable-temperature absorption spectra and fluorescence lifetime measurements were used to characterize the aggregation-induced absorption and emission in non-coordinating solvents. A selective aggregation-disaggregation process was also observed in thin films of this phthalocyanine zinc complex, and the optical properties of the film depend on the annealing temperature. The changes in the NIR region lead to a sizable visible color change that is recognizable by the naked human eye. The temperature-dependent control of the aggregation process in the thin film was confirmed using operando spectroscopy techniques.

One-step synthesis of ball-shaped metal complexes with a main absorption band in the near-IR region.

The design of near-IR materials is highly relevant to energy and pharmaceutical sciences due to the high proportion of near-IR irradiation in the solar spectrum and the high penetration of near-IR light in biological samples. Here, we show the one-step synthesis of hexacoordinated ruthenium and iron complexes that exhibit a main absorption band in the near-IR region. For that purpose, novel tridentate ligands were prepared by condensation of two diimines and four cyanoaryl derivatives in the presence of ruthenium and iron template ions. This method was applied to a wide variety of cyanoaryl, diimine, and metal ion combinations. The relationship between the structure and the optical and electrochemical properties in the resulting complexes was examined, and the results demonstrated that these compounds represent novel near-IR materials whose physical properties can be controlled based on rational design guidelines. The intense absorption bands in the 700-900 nm region were assigned to metal-to-ligand charge transfer (MLCT) transitions, which should allow applications in materials with triplet excited states under irradiation with near-IR light.

Chemoselective Synthesis of Aryloxy-Substituted Phthalocyanines.

The synthesis of the first examples of 8-fold α-aryloxy-substituted phthalocyanines is described. 3,6-Diiodophthalonitrile was used as a precursor for a series of 3,6-aryloxy-substituted phthalonitriles, and a lead-mediated macrocyclization was employed to afford the corresponding free-base phthalocyanine complexes. The optical, electrochemical, and aggregation properties of these complexes can be tuned by varying the substituents on the aryloxy groups or by changing the pH value.

(1,3)Pyrenophanes containing crown ether moieties as fluorescence sensors for metal and ammonium ions.

Crown ether containing (1,3)pyrenophanes 1-6 were synthesized, and UV absorption and fluorescence spectroscopic studies were carried out to determine their abilities to form complexes with metal and ammonium ions. The fluorescence spectra of 1.0 × 10-5 M solutions of 1, 2, 4 and 6 in 1 : 1 v/v CH2Cl2 : CH3CN were comprised of both monomer and intramolecular excimer emission bands, while only monomer emission bands were present in the fluorescence spectra of 3 and 5. The intensities of the intramolecular excimer emission bands of 1, 2, 4 and 6 in 1 : 1 v/v CH2Cl2 : CH3CN decreased and those of the monomer emission increased in conjunction with the existence of isoemissive points upon the addition of increasing concentrations of various metal perchlorates. The fluorescence spectral changes were dependent on the sizes of crown ether rings and metal ions and, as such, they reflected equilibrium constants for the formation of metal-crown ether complexes. Addition of n-Bu2NH2+PF6- or (PhCH2)2NH2+PF6- to the solutions of the (1,3)pyrenophane linked crown ethers, which brought about similar fluorescence spectral changes, led to the formation of pseudo-rotaxanes as was evidenced by an analysis of 1H NMR spectra and Job's plots. The fluorescence changes of 1 occurred during 5 cycles of repetitive addition and removal of Ba2+. The ratio of intensities of the monomer to the intramolecular excimer emission bands of 1, 2, 4 and 6 increased as the temperature decreased. Based on the experimental observations and the results of DFT calculations, it is concluded that the (1,3)pyrenophanes exist in solution as equilibrium mixtures of anti monomer emitting and syn intramolecular excimer emitting conformers and the equilibrium favors the anti form when the crown ether moieties form complexes with metal or ammonium ions.

Phototriggered Active Alkyne Generation from Cyclopropenones with Visible Light-Responsive Photocatalysts.

A photocatalytic active alkyne generation reaction was developed using cyclopropenone as a starting reagent. Visible light-responsive photocatalysts induced cyclopropenone decarbonylation. The resulting highly reactive alkyne could be used directly, without isolation, for further reactions, such as in a dehydration condensation reaction and alkyne-azide click chemistry.

Cationic axial ligands on sulfur substituted silicon(iv) phthalocyanines: improved hydrophilicity and exceptionally red-shifted absorption into the NIR region.

Herein, we report the exceptionally red-shifted absorption of sulfur-substituted silicon(iv) phthalocyanines upon introduction of cationic axial ligands. The Q band was red-shifted to approximately 900 nm with improved hydrophilicity by the combination of peripheral sulfur substituents and axial ammonium ligands. One such phthalocyanine exhibited remarkable photocytotoxicity upon irradiation with NIR light (∼810 nm) in live cells.