Synthesis of Unsymmetrically Condensed Benzo- and Thienotriazologermoles.

Germoles and siloles unsymmetrically condensed with heteroaromatic units are attracting much interest. In this study, compounds containing a triazologermole core unit condensed with a benzene or thiophene ring were prepared. Thienotriazologermole was subjected to bromination to obtain the bromide, which underwent transformation via the palladium-catalyzed Stille coupling reaction to form triphenylamine-substituted thienotriazolegermole, with an effective extension of conjugation. The electronic states and properties of these triazologermole derivatives are discussed on the basis of optical and electrochemical measurements and density functional theory calculations. Triphenylamine-substituted thienotriazolegermole showed clear solvatochromic properties in photoluminescence measurements, suggesting that intramolecular charge transfer occurs at the photo-excited state. This clearly indicates that the triazologermole unit is useful as an acceptor of donor-acceptor compounds. The potential application of triphenylamine-substituted thienotriazolegermole as a sensing material was also explored.

Synthesis and Properties of Boron-Containing Heteromerous Bistricyclic Aromatic Enes: Structural Effects on Thermodynamic Stability and Photoreactivity.

Overcrowded bistricyclic aromatic enes (BAEs) have several conformations such as twisted and anti-folded conformers, and their stereochemistry and chromism have been studied in earnest. In this study, boron-containing heteromerous BAEs having various tricyclic structures were synthesized and their photophysical properties investigated. Single-crystal X-ray analysis revealed that the introduction of a rigid fluorene unit resulted in a twisted conformer, whereas the introduction of flexible units such as thioxanthene and 9,9-dimethyl-9,10-dihydroanthracene units resulted in an anti-folded conformer. The absorption spectra of the heteromerous BAEs were dependent on the introduced tricyclic structures, suggesting the immense impact of the tricyclic structures on the electronic structures of BAEs. DFT calculations revealed the large effect of the flexibility of the tricyclic structures on the thermodynamic stability of the conformers. In addition, the boron-containing heteromerous BAEs underwent photocyclization reactions, indicating their potential application as precursors of polyaromatic hydrocarbons and helical aromatic materials.

Robust and Transparent Antifogging Polysilsesquioxane Film Containing a Hydroxy Group.

Poly(glycidyloxypropyl)silsesquioxane (PGPS) was successfully synthesized by hydrolysis and polycondensation using the nitrogen flow method. A poly(3-(2,3-dihydroxypropoxypropyl)silsesquioxane) (PSQ-OH) film was prepared via two routes. In route A, PSQ-OH was prepared by the hydrolysis of the epoxy group of PGPS in an aqueous hydrochloric acid (HCl)/tetrahydrofuran solution, affording a diol group; then, PSQ-OH was coated on a glass substrate and heated. The antifogging performance of the PSQ-OH film was evaluated in terms of water uptake (WU) and scratch resistance. The obtained PSQ-OH film exhibited a low WU of 5% and a scratch resistance of 1.6. In route B, PGPS was coated on a glass substrate and immersed in a 0.5 mol/L aqueous sulfuric acid solution for 1-15 h at room temperature, producing a diol group. The solid-state 13C nuclear magnetic resonance spectrum indicated that the epoxy group was completely hydrolyzed after immersion for 15 h. The WU of the PSQ-OH film prepared via route B increased from 5 to 19% with the increase in the immersion time and was higher than that of the PSQ-OH film prepared via route A. The PSQ-OH film on a glass substrate retained transparency under water vapor exposure at 60 °C. The PSQ-OH film prepared via route B exhibited a high scratch resistance of 2.7-3.6, similar to that of a poly(3-(2-aminoethylaminopropyl)silsesquioxane) film. The scratch resistance of the PSQ-OH film was 5-7 times higher than that of the poly(vinyl alcohol) film. The PSQ-OH film was uniform with no pinholes and cracks. The PSQ-OH film was transparent and colorless and exhibited a high transmittance of >90% in the wavelength range of 400-800 nm. Overall, the prepared PSQ-OH film exhibits good antifogging, transparency, and mechanical properties.

Optical Characteristics of Hybrid Macrocycles with Dithienogermole and Tricoordinate Boron Units.

The introduction of unconventional elements into π-conjugated systems has been studied to manipulate the electronic states and properties of compounds. Herein, boron- and germanium-containing hybrid macrocycles, as a new class of element-hybrid conjugated systems, have been synthesized. The palladium-catalyzed Stille cross coupling of bis(bromothienyl)borane and bis(trimethylstannylthienyl)- or bis(trimethylstannylphenyl)-substituted dithienogermoles as the boron- and germanium-containing building blocks, respectively, produced a mixture of several macrocyclic compounds. Single-crystal X-ray analysis of the 2:2 coupling product revealed a planar structure with a cavity inside the macrocycle. The optical properties of the macrocyclic products indicated rather small electronic interactions between the building units. However, intramolecular photoenergy transfer from the dithienogermole unit to the boron unit was clearly observed with respect to the fluorescence spectra.

Asymmetric Synthesis of Bridged N-Heterocycles with Tertiary Carbon Center through Barbas Dienamine-Catalysis: Scope and Applications.

A direct aza-Diels-Alder reaction between 2-aryl-3H-indolin-3-ones and cyclic-enones has been developed to access chiral indolin-3-one fused polycyclic bridged compounds. This method proceeds via proline-catalyzed Barbas-dienamine intermediate formation from various cyclic-enones such as 2-cyclopenten-1-one, 2-cyclohexene-1-one, and 2-cycloheptene-1-one, followed by a reaction with 2-aryl-3H-indol-3-ones. Several indolin-3-ones fusing [2.2.2], [2.2.1], and [3.2.1] skeletons decorated with a tertiary carbon chiral center have been prepared. Computational studies (DFT) supported the observed stereoselectivity in the method. The synthesized compounds have shown exciting photophysical activities and selective sensing of Pd2+ and Fe3+ ions through the fluorescence quenching "switch-off" mode.

Direct Amine-Catalyzed Enantioselective Synthesis of Pentacyclic Dibenzo[b,f][1,4]oxazepine/Thiazepine-Fused Isoquinuclidines along with DFT Calculations.

A direct protocol for the asymmetric synthesis of dibenzoxazepine/thiazepine-fused [2.2.2] isoquinuclidines is developed. The reaction proceeds through a proline-catalyzed direct Mannich reaction followed by an intramolecular aza-Michael cascade sequence between 2-cyclohexene-1-one and various tricyclic imines, like dibenzoxazepines/thiazepines, as an overall [4 + 2] aza-Diels-Alder reaction. A series of pentacyclic isoquinuclidines have been prepared, with complete endo-selectivity, in good to high yields and excellent enantioselectivity (>99:1). Density functional theory (DFT) calculations further support the observed high stereochemical outcome of the reaction.

Intramolecular Energy Transfer in Dithienogermole Derivatives.

Dithienogermole (DTG) has been applied as a useful building unit of optical/semiconducting materials for organic optoelectronic devices because of its extended conjugation, high chemical stability, and good emissive properties. Although DTG has two substituents on the Ge atom, the substituents have been limited to simple alkyl and aryl groups in previous work. In this work, to further uncover the new functionalities of this useful building unit, various π-conjugated groups were introduced on Ge of DTG. It was expected that the introduction of π-conjugated groups would give rise to efficient energy transfer between the substituents and the DTG core, which are in proximity and linked by a Ge atom. The thus-prepared DTG compounds with fluorene, terthiophene, and pyrene units on Ge possessed well-separated frontier orbitals on the substituents and the DTG core, as proved by the absorption spectra and DFT calculations. The substituted DTG derivatives showed clear emission only from the energy acceptor even though the energy donor was photoexcited. This indicated the highly efficient energy transfer in these compounds. We also prepared more π-extended compound DTGFl2-Ph with phenyl groups on the DTG thiophene rings. DTGFl2-Ph showed strong emission in the visible region with efficient energy transfer properties. These results clearly indicate the potential application of the present DTG system as optical functional materials.

Luminescent Di- and Tetranuclear Gold Complexes of Bis(diphenylphosphinyl)-Functionalized Dipyrido-Annulated N-Heterocyclic Carbene.

Phosphine-functionalized N-heterocyclic carbene (NHC) ligands are known to complex group 11 metal centers to form multinuclear complexes with photoluminescence properties. This study reports a structurally rigid ortho-substituted dipyrido-annulated NHC with T-shape coordination geometry and its di- and tetranuclear gold(I) complexes. The free ligand as well as all metal complexes are found luminescent at room temperature and phosphorescent at 77 K. Although metal d10-d10 interactions are evident based on their solid-state structures, their effect on the photoemission is limited, most likely due to the weak coordination of the ligand to the metal centers in solution.

Synthesis and optical and electrochemical properties of a phenanthrodithiophene (fused-bibenzo[c]thiophene) derivative.

We designed and developed a fused-bibenzo[c]thiophene, namely, 2,9-bis(tert-butyldimethylsilyl)phenanthro[9,8-bc:10,1-b'c']dithiophene (PHDT-Si), as a new π-building block in the emitters, photosensitizers and semiconductors for organic optoelectronic devices. Based on photophysical (photoabsorption, fluorescence and time-resolved fluorescence spectroscopy) and electrochemical measurements (cyclic voltammetry), and density functional theory (DFT) calculations, this work reveals that the fused-bibenzo[c]thiophene PHDT-Si, which is prepared by an efficient synthesis method, has a rigid, high planar and expanded π-conjugation structure, and possesses intense photoabsorption and fluorescence properties (λ = 598 nm (εmax = 41 000 M-1 cm-1) and λ = 613 nm (Φf = 0.74) in toluene) in the long-wavelength region and undergoes an electrochemically reversible oxidation process, compared to non-fused 1,1'-bis(tert-butyldimethylsilyl)-4,4'-bibenzo[c]thiophene (BBT-Si).

Synthesis and optical and electrochemical properties of julolidine-structured pyrido[3,4-b]indole dye.

The julolidine-structured pyrido[3,4-b]indole dye ET-1 has been newly designed and developed as a small D-A fluorescent dye. ET-1 showed bathochromic shifts of the fluorescence band upon changing from aprotic solvents to protic solvents, as well as positive fluorescence solvatochromism. Moreover, it was found that ET-1 can form a 1 : 1 Py(N)-B complex with boron trifluoride and a hydrogen-bonded proton transfer (Py(N)-H) complex with trifluoroacetic acid, which exhibit photoabsorption and fluorescence bands at a longer wavelength region than the pristine ET-1. Based on optical (photoabsorption and fluorescence spectroscopy) and electrochemical (cyclic voltammetry) measurements, Lippert-Mataga plots, 1H NMR spectral measurement and density functional theory (DFT) calculation, this work indicated that the Py(N)-B complex or the Py(N)-H complex is effectively formed and stable in solution. This is due to the strong Py(N)-B interaction or Py(N)-hydrogen-bond, which can be attributed to the enhanced basicity or the accumulated electron density on the nitrogen atom of the pyridine ring caused by the introduction of a julolidine (quinolizidine) moiety as a strong electron-donating group. We propose that the D-A-type dye ET-1 based on the julolidine-structured pyrido[3,4-b]indole possesses the ability to act as a calorimetric and fluorescent sensor for Brønsted and Lewis acids.

Group 14 Dithienometallole-Linked Ethynylene-Conjugated Porphyrin Dimers.

The considerably conjugated π systems of the group 14 dithienometallole-linked ethynylene-conjugated porphyrin dimers (1Ms) were described based on comprehensive experimental and theoretical studies. The electronic absorption spectra of 1M displayed a large splitting in the Soret band and a red-shifted Q-band, indicating that the dithienometallole spacer was effective in facilitating the porphyrin-porphyrin electronic coupling. Torsional planarization behaviors of 1M were observed in the time-resolved fluorescence spectra. Density functional theory (DFT) calculations revealed that the dithienometallole spacer is an ideal partner for the ethynylene-conjugated porphyrin to produce fully delocalized highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels due to their similar HOMO and LUMO levels. Finally, 1M exhibited a strong propensity for the quinoidal-cummulenic conjugation in the dithienometallole spacer when in a photoexcited state.

Impact of the molecular structure and adsorption mode of D-π-A dye sensitizers with a pyridyl group in dye-sensitized solar cells on the adsorption equilibrium constant for dye-adsorption on TiO2 surface.

D-π-A dyes NI-4 bearing a pyridyl group, YNI-1 bearing two pyridyl groups and YNI-2 bearing two thienylpyridyl groups as the anchoring group on the TiO2 surface have been developed as dye sensitizers for dye-sensitized solar cells (DSSCs), where NI-4 and YNI-2 can adsorb onto the TiO2 electrode through the formation of the coordinate bond between the pyridyl group of the dye and the Lewis acid site (exposed Tin+ cations) on the TiO2 surface, but YNI-1 is predominantly adsorbed on the TiO2 electrode through the formation of the hydrogen bond between the pyridyl group of the dye and the Brønsted acid sites (surface-bound hydroxyl groups, Ti-OH) on the TiO2 surface. The difference in the dye-adsorption mode among the three dyes on the TiO2 surface has been investigated from the adsorption equilibrium constant (Kad) based on the Langmuir adsorption isotherms. It was found that the Kad values of YNI-1 and YNI-2 are higher than that of NI-4, and more interestingly, the Kad value of YNI-2 is higher than that of YNI-1. This work demonstrates that that for the D-π-A dye sensitizers with the pyridyl group as the anchoring group to the TiO2 surface the number of pyridyl groups and the dye-adsorption mode on the TiO2 electrode as well as the molecular structure of the dye sensitizer affect the Kad value for the adsorption of the dye to the TiO2 electrode, that is, resulting in a difference in the Kad value among the D-π-A dye sensitizers NI-4, YNI-1 and YNI-2.

Development of type-I/type-II hybrid dye sensitizer with both pyridyl group and catechol unit as anchoring group for type-I/type-II dye-sensitized solar cell.

A type-I/type-II hybrid dye sensitizer with a pyridyl group and a catechol unit as the anchoring group has been developed and its photovoltaic performance in dye-sensitized solar cells (DSSCs) is investigated. The sensitizer has the ability to adsorb on a TiO2 electrode through both the coordination bond at Lewis acid sites and the bidentate binuclear bridging linkage at Brønsted acid sites on the TiO2 surface, which makes it possible to inject an electron into the conduction band of the TiO2 electrode by the intramolecular charge-transfer (ICT) excitation (type-I pathway) and by the photoexcitation of the dye-to-TiO2 charge transfer (DTCT) band (type-II pathway). It was found that the type-I/type-II hybrid dye sensitizer adsorbed on TiO2 film exhibits a broad photoabsorption band originating from ICT and DTCT characteristics. Here we reveal the photophysical and electrochemical properties of the type-I/type-II hybrid dye sensitizer bearing a pyridyl group and a catechol unit, along with its adsorption modes onto TiO2 film, and its photovoltaic performance in type-I/type-II DSSC, based on optical (photoabsorption and fluorescence spectroscopy) and electrochemical measurements (cyclic voltammetry), density functional theory (DFT) calculation, FT-IR spectroscopy of the dyes adsorbed on TiO2 film, photocurrent-voltage (I-V) curves, incident photon-to-current conversion efficiency (IPCE) spectra, and electrochemical impedance spectroscopy (EIS) for DSSC.

Site-Specific Electron-Relaxation Caused by Si:2p Core-Level Photoionization: Comparison between F3SiCH2CH2Si(CH3)3 and Cl3SiCH2CH2Si(CH3)3 Vapors by Means of Photoelectron Auger Electron Coincidence Spectroscopy.

Site-specific electron relaxations caused by Si:2p core-level photoionizations in F3SiCH2CH2Si(CH3)3 and Cl3SiCH2CH2Si(CH3)3 vapors have been studied by means of the photoelectron Auger electron coincidence spectroscopy. F3SiCH2CH2Si(CH3)3 shows almost 100% site-specificity in fragmentation caused by the Si:2p ionization. However, substitution of Cl for F of F3SiCH2CH2Si(CH3)3 considerably reduces the site-specificity at the Si atom bonded to three halogen atoms, with the site-specificity at the Si site bonded to three methyl groups remaining largely unchanged. The site-specificity reduction in Cl3SiCH2CH2Si(CH3)3 is considered to take place during the transient period between Si:L23VV Auger electron emission and the subsequent fragmentation. The reason for the reduction can be explained in terms of some differences between these two molecules in the L23VV Auger decay at the Si site bonded to the three halogen atoms.

Synthesis of a Conjugated D-A Polymer with Bi(disilanobithiophene) as a New Donor Component.

A new conjugated donor-acceptor (D-A) polymer pDSBT2-BT containing bi(disilano-bisthiophene) and benzothiadiazole as donor and acceptor units, respectively, was prepared. The polymer showed a broad UV-vis absorption band at λmax = 599 nm in chlorobenzene. The absorption band was shifted to λmax = 629 nm when the polymer was measured as a film, indicating enhanced interchain interactions of the polymer. Bulk hetero-junction polymer solar cells (BHJ-PSCs) were fabricated using pDSBT2-BT and PC71BM as host and guest materials, respectively. Optimization of cell fabrication conditions provided a maximal power conversion efficiency of 3.3% and the following cell parameters: Voc = 0.86 V, Jsc = 7.56 mA/cm², and FF = 0.51. Although the efficiency still leaves much to be desired, these data underscore the potential of pDSBT2-BT as a high-voltage polymer solar cell material.

Effect of Substituents in Catechol Dye Sensitizers on Photovoltaic Performance of Type II Dye-Sensitized Solar Cells.

In order to provide a direction in molecular design of catechol (Cat) dyes for type II dye-sensitized solar cells (DSSCs), the dye-to-TiO2 charge-transfer (DTCT) characteristics of Cat dyes with various substituents and their photovoltaic performance in DSSCs are investigated. The Cat dyes with electron-donating or moderately electron-withdrawing substituents exhibit a broad absorption band corresponding to DTCT upon binding to TiO2 films, whereas those with strongly electron-withdrawing substituents exhibit weak DTCT. This study indicates that the introduction of a moderately electron-withdrawing substituent on the Cat moiety leads to not only an increase in the DTCT efficiency, but also the retardation of back electron transfer. This results in favorable conditions for the type II electron-injection pathway from the ground state of the Cat dye to the conduction band of the TiO2 electrode by the photoexcitation of DTCT bands.

Phosphorescence Properties of Boron/Bismuth Hybrid Conjugated Materials.

By introducing main-group elements such as boron and bismuth to π-conjugated systems, it is possible to modify the optical properties of π-conjugated materials through orbital interactions between the orbital on the elements and π/π*-orbitals, and the heavy atom effect. Moreover, bismuth, which is the heaviest stable element, induces a significant heavy atom effect, making organobismuth compounds promising for applications as phosphorescent materials. In this study, we synthesized new room-temperature phosphorescent materials by incorporating bismuth into thiophene units. The phosphorescence properties of these materials, such as emission lifetime and wavelength, could be further controlled by combining tricoordinate boron with the thienylbismuth structures. The synthesized bismuth- and boron-containing thiophene compounds exhibited phosphorescence at room temperature in both solution and solid states. Furthermore, the introduction of boron raised the energy of the triplet state in the π-conjugated system, resulting in a blue shift of the phosphorescence wavelength. The analysis of photoluminescence properties and TD-DFT calculations revealed that the introduction of bismuth enhances phosphorescence properties, whereas the introduction of boron further promotes intersystem crossing.

Insights into mechanistic interpretation of crystalline-state reddish phosphorescence of non-planar π-conjugated organoboron compounds.

Metal-free room-temperature phosphorescent (RTP) materials are attracting attention in such applications as organic light-emitting diodes and bioimaging. However, the chemical structures of RTP materials reported thus far are mostly predominantly based on π-conjugated systems incorporating heavy atoms such as bromine atoms or carbonyl groups, resulting in limited structural diversity. On the other hand, triarylboranes are known for their strong Lewis acidity and deep LUMO energy levels, but few studies have reported on their RTP properties. In this study, we discovered that compounds based on a tetracyclic structure containing boron, referred to as benzo[d]dithieno[b,f]borepins, exhibit strong solid-state reddish phosphorescence even in air. Quantum chemical calculations, including those for model compounds, revealed that the loss of planarity of the tetracyclic structure increases spin-orbit coupling matrix elements, thereby accelerating the intersystem crossing process. Moreover, single-crystal X-ray structural analysis and natural energy decomposition analysis suggested that the borepin compounds without bromine or oxygen atoms, unlike typical RTP materials, exhibit red-shifted phosphorescence in the crystalline state owing to structural relaxation in the T1 state. Additionally, the borepin compounds showed potential application as bioimaging dyes.

Highly luminescent antiaromatic diborinines with fused thiophene rings.

Tricoordinate boron-incorporated π-conjugated systems are widely investigated as optoelectronic materials because of their unique p-π* orbital interactions and high Lewis acidity. Among them, thiophene-fused diborinines are characterized by moderate antiaromaticity and extended conjugation. In this work, we have developed two new dithienodiborinines with C2h and C2v symmetries, which exhibited completely different optical properties. The thiophene-fused diborinines synthesized in this study showed excellent fluorescence properties both in solution and in the solid state, with quantum yields of up to 95%. The high antiaromaticity enhanced the Lewis acidity of the boron centers, as proven by the large association constants with fluoride ion estimated from titration experiments. The high Lewis acidity and the superior luminescence property have enabled their application as fluorescent sensor materials for the detection of ammonia vapor.

Intermolecular distances of carboxylated TEMPO derivatives on TiO2 evaluated by spin-probe ESR.

Nearest-neighbor intermolecular distances of molecules adsorbed on the surface of nanocrystalline TiO(2) particles were evaluated by the electron spin resonance (ESR) technique with molecules having a nitroxide radical and a carboxyl group as a spin probe to clarify their aggregation behaviors on TiO(2) and the influence of coadsorbates.