Access to optically active tetrafluoroethylenated amines based on [1,3]-proton shift reaction.

Treatment of various ()--(2,2,3,3-tetrafluoropent-4-en-1-ylidene)-1-phenylethylamine derivatives with 2.4 equiv of DBU in toluene at room temperature to 50 °C for 24 h led to a smooth [1,3]-proton shift reaction with a high chirality transfer, affording the corresponding rearranged products in acceptable yields. Without purification, these products were subjected to acid hydrolysis and the subsequent -Cbz protection, providing the optically active tetrafluoroethylenated amides in moderate three-step yields.

Photoluminescence color-tuning with polymer-dispersed fluorescent films containing two fluorinated diphenylacetylene-type fluorophores.

The development of organic light-emitting devices has driven demand for new luminescent materials, particularly after the 2001 discovery of aggregation-induced emission. This study focuses on fluorinated diphenylacetylene-based luminescent molecules, revealing that specific molecular modifications can enhance fluorescence and achieve a wide range of photoluminescence colors. A simple and effective luminescence color-tuning method is proposed to investigate the photoluminescence behavior of two-component polymer dispersion films blended with two types of fluorinated diphenylacetylenes, namely blue- and yellow- or red-fluorescent fluorinated diphenylacetylenes.

Experimental and Theoretical Studies on Cobalt-Catalyzed Regioselective Hydrosilylation of Tetrafluorinated Cyclohexa-1,3-dienes.

Cyclohexa-1,3-dienes bearing a tetrafluoroethylene group underwent highly regioselective hydrosilylation in the presence of 1-10 mol % Co(CO) in 1,2-dichloroethane under mild conditions (reflux, 3 h), which led to an abundant yield of homoallylsilanes. Mechanistic studies proved that the reaction proceeds as per the modified Chalk-Harrod mechanism; via DFT calculation, the reason for homoallylsilanes being exclusively obtained was demonstrated. The formal synthesis of a tetrafluorinated negative-type liquid crystal demonstrated the synthetic utility of such hydrosilylation.

Diverse Synthetic Transformations Using 4-Bromo-3,3,4,4-tetrafluorobut-1-ene and Its Applications in the Preparation of CF CF -Containing Sugars, Liquid Crystals, and Light-Emitting Materials.

Organic molecules with fluoroalkylene scaffolds, especially a tetrafluoroethylene (CF CF ) moiety, in their molecular structures exhibit unique biological activities, or can be applied to functional materials such as liquid crystals and light-emitting materials. Although several methods for the syntheses of CF CF -containing organic molecules have been reported to date, they have been limited to methods using explosives and fluorinating agents. Therefore, there is an urgent need to develop simple and efficient approaches to synthesize CF CF -containing organic molecules from readily available fluorinated substrates using carbon-carbon bond formation reactions.

Donor-π-Acceptor-Type Fluorinated Tolane Containing a Semifluoroalkoxy Chain as a Condensed-Phase Luminophore.

Photoluminescent liquid-crystalline (PLLC) molecules, which can easily tune the PL behavior through the crystal (Cry)-LC phase transition, have attracted significant attention. Previously, we have demonstrated that the incorporation of a semifluoroalkoxy chain into π-conjugated mesogen is a promising approach for developing PLLC molecules with PL and SmA LC characteristics. We focused on the LC and PL characteristics of the molecules induced by the semifluoroalkoxy chain and fluorinated tolanes in the condensed phase.

Development of Yellow-to-Orange Photoluminescence Molecules Based on Alterations in the Donor Units of Fluorinated Tolanes.

Since the aggregation-induced emission (AIE) phenomenon was first reported by Tang et al., much effort has been devoted to the development of solid-state luminescent molecules by chemists worldwide. Our group successfully developed fluorinated tolanes as novel compact π-conjugated luminophores with blue photoluminescence (PL) in the crystalline state.

Practical Synthesis of -Trifluoromethylated Pyridines Based on Regioselective Cobalt-Catalyzed [2+2+2] Cycloaddition using Trifluoromethylated Diynes with Nitriles.

Regioselective cobalt-catalyzed [2+2+2] cycloaddition using fluorine-containing diynes with nitriles was described. Cycloaddition of fluorinated diynes with nitriles under the influence of CoCl(phen), zinc bromide, and zinc dust in dichloroethane at 80°C for 3 h took place smoothly, exclusively affording the corresponding -fluoroalkylated pyridines in excellent yields. In addition, dinitriles as substrate were also found to be suitable for this reaction, giving the corresponding fluoroalkylated bipyridine derivatives in excellent yields.

Systematic Studies on the Effect of Fluorine Atoms in Fluorinated Tolanes on Their Photophysical Properties.

In this study, we synthesized a series of fluorinated and non-fluorinated tolanes, in which one or more fluorine atoms were systematically introduced into one aromatic ring of a tolane scaffold, and systematically evaluated their photophysical properties. All the tolanes with or without fluorine substituents were found to have poor photoluminescence (PL) in tetrahydrofuran (THF) solutions. On the other hand, in the crystalline state, non-fluorinated and fluorinated tolanes with one or four fluorine atoms were less emissive, whereas fluorinated tolanes with three or five fluorine atoms exhibited high PL efficiencies (Ф) up to 0.

Cobalt-Catalyzed C-H Activation/Annulation of Benzamides with Fluorine-Containing Alkynes: A Route to 3- and 4-Fluoroalkylated Isoquinolinones.

The C-H activation/annulation reaction of various benzamides with fluoroalkylated alkynes in the presence of a Co(acac)·2HO catalyst proceeded very smoothly to give the corresponding 3- and 4-fluoroalkylated isoquinolinones in excellent yields with approximately 70% regioselectivities. These regioisomers could be successfully separated and obtained in pure form. Major or minor regioisomers were determined as 4- or 3-fluoroalkylated isoquinolinones, respectively, based on X-ray crystallographic analyses.

Regioselective cobalt(II)-catalyzed [2 + 3] cycloaddition reaction of fluoroalkylated alkynes with 2-formylphenylboronic acids: easy access to 2-fluoroalkylated indenols.

[2 + 3] cycloaddition reactions of fluorinated alkynes with 2-formylphenylboronic acids under the influence of Co(acac)·2HO in two-component solvents of acetonitrile/2-propanol at reflux temperature for 18 h took place smoothly, affording the corresponding fluoroalkylated indenol derivatives in good yields. This reaction shows excellent regioselectivity, giving 2-fluoroalkylated indenols, together with a very small amount of 3-fluoroalkylated indanones as side products.

Excited-State Dynamics of Room-Temperature Phosphorescent Organic Materials Based on Monobenzil and Bisbenzil Frameworks.

Room-temperature phosphorescent (RTP) materials have been attracting tremendous interest, owing to their unique material characteristics and potential applications for state-of-the-art optoelectronic devices. Recently, we reported the synthesis and fundamental photophysical properties of new RTP materials based on benzil, i.e.

Development of fluorinated benzils and bisbenzils as room-temperature phosphorescent molecules.

Pure organic phosphorescent molecules are attractive alternatives to transition-metal-complex-based phosphores for biomedical and technological applications owing to their abundance and nontoxicity. This article discloses the design, synthesis, and photophysical properties of fluorinated benzil and bisbenzil derivatives as potential pure organic room-temperature phosphorescent molecules. These compounds were separately converted from the corresponding fluorinated bistolanes via PdCl-catalyzed oxidation by dimethyl sulfoxide, while nonfluorinated bistolane provided the corresponding bisbenzil derivatives exclusively in a similar manner.

Novel V- and Y-Shaped Light-Emitting Liquid Crystals with Pentafluorinated Bistolane-Based Luminophores.

Herein, we describe the synthesis of novel light-emitting liquid-crystalline (LC) compounds bearing pentafluorinated bistolane-based luminophores with a V- or a Y-shaped molecular geometry and the evaluation of their LC and photophysical characteristics. The V- or Y-shaped compounds exhibited a unique LC phase and showed photoluminescence (PL) behavior under various circumstances, such as in dilute solution or in the solid state. Notably, PL characteristics were observed even under high-temperature conditions with a crystal (Cr) to LC phase transition, although the PL efficiency ( ) was gradually reduced because of thermal molecular motion.

Development of Novel Solid-State Light-Emitting Materials Based on Pentafluorinated Tolane Fluorophores.

We herein describe the synthesis of novel pentafluorinated tolane fluorophores, which possess an extended π-conjugated structure with a large molecular dipole moment along the longitudinal axis. We also report a detailed evaluation of both the photophysical and thermal behaviors of these fluorophores. All molecules displayed photoluminescence (PL) characteristics in both the crystalline state and in dilute solutions.

Synthesis and characterization of bent fluorine-containing donor-π-acceptor molecules as intense luminophores with large Stokes shifts.

Herein, we prepared novel bent fluorine-containing donor-π-acceptor (D-π-A) molecules from commercially available octafluorocyclopentene using a facile two-step procedure, revealing that the above molecules absorb UV-light and exhibit yellow photoluminescence (PL) with high PL efficiencies (ΦPL) in solution. The corresponding Stokes shifts exceeded 10 000 cm-1, and the maximum PL wavelength (λPL) strongly depended on solvent polarity or intermolecular interactions in the solid state. On the basis of a Lippert-Mataga plot, PL was confidently assigned to radiative relaxation from an intramolecular charge-transfer excited state.

Stabilization of SF with Glyme-Coordinated Alkali Metal Cations.

The stabilization of complex fluoroanions derived from weakly acidic parent fluorides is a significant and ongoing challenge. The [SF] anion is recognized as one such case, and only a limited number of [SF] salts are known to be stable at room temperature. In the present study, glyme-coordinated alkali metal cations (K, Rb, and Cs) are employed to stabilize [SF], which provides a simple synthetic route to a [SF] salt.

Practical tetrafluoroethylene fragment installation through a coupling reaction of (1,1,2,2-tetrafluorobut-3-en-1-yl)zinc bromide with various electrophiles.

(1,1,2,2-Tetrafluorobut-3-en-1-yl)zinc bromide was prepared by insertion of the zinc-silver couple into the CF-Br bond of commercially available 4-bromo-3,3,4,4-tetrafluorobut-1-ene in DMF at 0 °C for 0.5 h, The resultant polyfluorinated zinc reagent was found to be thermally stable at ambient temperature and storable for at least 1.5 years in the refrigerator.

Thermoresponsive luminescence properties of polyfluorinated bistolane-type light-emitting liquid crystals.

We developed and characterized four polyfluorinated bistolane derivatives. These compounds, which possess either two alkoxy substituents or an alkoxy group and a bromine atom in their two molecular terminals, were synthesized from readily available 4-alkoxy-1-ethynylbenzene with a facile three-step procedure. Their thermodynamic and photophysical properties were evaluated in detail, and they were found to display both liquid-crystalline (LC) and photoluminescence properties.

Gram-scale preparation of negative-type liquid crystals with a CFCF-carbocycle unit via an improved short-step synthetic protocol.

Herein, we demonstrate an improved short-step protocol for the synthesis of multicyclic molecules having a CFCF-containing cyclohexadiene or cyclohexane framework in a mesogenic structure. These molecules are promising candidates for vertical alignment (VA)-mode liquid crystal (LC) display devices owing to their large negative dielectric constant. The tetrafluorinated multicyclic molecules were successfully obtained in only five or six reaction steps without the need for special handling techniques, as is generally required for thermally unstable organometallic species, representing a reduction of three reaction steps.

Rational design and synthesis of a novel laterally-tetrafluorinated tricyclic mesogen with large negative dielectric anisotropy.

Guided by theoretical calculations, we predicted that 5,5,6,6-tetrafluoro-1-methoxycyclohex-1-ene, a new structural motif, exhibits a large negative dielectric anisotropy, and then developed a synthetic strategy for the preparation of the novel tetrafluorinated tricyclic mesogen in twelve reaction steps starting from a commercially available fluorinated starting material. During the evaluation of its liquid-crystalline characteristics, the tetrafluorinated mesogen was found to display low birefringence and a large negative dielectric anisotropy, confirming that its molecular structure is a reasonable design for the further development of novel mesogenic molecules with large negative dielectric anisotropies.

Fluorine-containing bistolanes as light-emitting liquid crystalline molecules.

We synthesised a series of dissymmetric bistolane derivatives and evaluated their liquid-crystalline (LC) and photoluminescence properties in detail. In measuring LC behaviours, rational structural design based on the dissymmetric molecular structure and electron-density distribution facilitated the production of the LC phase with a wide temperature range (up to 97 °C). In addition, dissymmetric bistolane derivatives were shown to strongly emit blue-photoluminescence in dilute solution and in crystalline states.

Stereochemically Defined Various Multisubstituted Alkenes Bearing a Tetrafluoroethylene (-CFCF-) Fragment.

Highly regio- and stereoselective transformation of commercially available 4-bromo-3,3,4,4-tetrafluoro-1-butene into multisubstituted alkenes having a tetrafluoroethylene fragment through Heck reactions and/or Suzuki-Miyaura cross-coupling reactions was established. Thus, the obtained alkenes underwent a smooth reductive coupling reaction with aldehydes under the influence of MeLi/LiBr-free, affording structurally unprecedented fluorinated materials.

Unusual reaction behavior of gem-difluorocyclopropane derivatives: stereoselective synthesis of β-monofluoroallylic alcohols, ethers, esters, and amide.

On treating gem-difluorocyclopropylstannanes, derived from the radical hydrostannation of gem-difluorocyclopropenes, with 1.5 equiv of MeLi in THF at -78 °C for 5 min, followed by quenching the reaction with various agents, such as H2O, alcohols, carboxylic acids, and tosylamide, the corresponding β-fluoroallylic alcohols, ethers, esters, and amide were obtained with exclusive Z-selectivity in acceptable yields.