Design, Regioselective Synthesis, and Photophysical Properties of Perfluoronaphthalene-Based Donor-Acceptor-Donor Fluorescent Dyes.

A one-step route to a series of perfluoronaphthalene-based donor (D)-acceptor (A)-D fluorescent dyes with various electron-donating groups was developed. The perfluoronaphthalene moiety in the D-A-D dyes served as a good electron-accepting aromatic ring with excellent intramolecular charge transfer properties, as determined by density functional theory calculations and measurements of the fluorescence properties in solution, in poly(methyl methacrylate) (PMMA) films, and in crystal form. Notably, replacing the naphthalene ring with perfluoronaphthalene in the D-A-D dyes carrying the phenothiazine moiety not only stabilized the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels but also reduced the energy band gap to change the emission color from blue to yellow. Among the four synthesized perfluoronaphthalene D-A-D dyes, those bearing diphenylamino groups afforded the best fluorescence quantum yields in Et2O solution (0.60) and in PMMA film (0.65) because the propeller structure of the diphenylamino group that acts as a donor substituent effectively suppresses radiation-free deactivation. In contrast, in the crystalline state, the carbazoyl-bearing D-A-D dye provided the best fluorescence quantum yield (0.35) because the radiation-free inactivation was suppressed by π-πF stacking at the donor site, which was confirmed by single-crystal X-ray analysis.

Practical Synthesis of α-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 CoCl2(phen), zinc bromide, and zinc dust in dichloroethane at 80°C for 3 h took place smoothly, exclusively affording the corresponding α-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.

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)2·2H2O 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.

Fused-Nonacyclic Multi-Resonance Delayed Fluorescence Emitter Based on Ladder-Thiaborin Exhibiting Narrowband Sky-Blue Emission with Accelerated Reverse Intersystem Crossing.

Developing organic luminophores with unique capability of strong narrowband emission is both crucial and challenging for the further advancement of organic light-emitting diodes (OLEDs). Herein, a nanographitic fused-nonacyclic π-system (BSBS-N1), which was strategically embedded with multiple boron, nitrogen, and sulfur atoms, was developed as a new multi-resonance thermally activated delayed fluorescence (MR-TADF) emitter. Narrowband sky-blue emission with a peak at 478 nm, full width at half maximum of 24 nm, and photoluminescence quantum yield of 89 % was obtained with BSBS-N1. Additionally, the spin-orbit coupling was enhanced by incorporating two sulfur atoms, thereby facilitating the spin-flipping process between the excited triplet and singlet states. OLEDs based on BSBS-N1 as a sky-blue MR-TADF emitter achieved a high maximum external electroluminescence quantum efficiency of 21.0 %, with improved efficiency roll-off.

Syntheses of α-CF3-α-quaternary ketones via p-quinone methides and their derivatization to compounds with successively congested stereogenic centers.

New and successful results for the construction of new and structurally interesting compounds are reported via N-heterocyclic carbene (NHC)-catalyzed 1,6-conjugate additions of a variety of aldehydes to δ-CF3-δ-substituted p-quinone methides generated in situ, and the products are used for the 1,2-addition reactions of appropriate metal nucleophiles, enabling us to furnish highly diastereoselective products with a unique successive quaternary carbon-tertiary alcohol framework (up to dr = >99 : 1).

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. Moreover, the synthesized luminophores showed intense PL even in the crystalline state and exhibited alkoxy chain length-dependent PL behavior (e.g., high ΦPL, λPL = 486-540 nm).

Syntheses and Structures of d10 Coinage Metal Complexes of Electron-Accepting Phosphine Ligands Featuring a 3,3,4,4,5,5-Hexafluorocyclopentene Framework.

Cu(I), Ag(I), and Au(I) complexes of monophosphine or bisphosphine ligands based on the 3,3,4,4,5,5-hexafluorocyclopentene skeleton were synthesized and structurally characterized by X-ray crystallographic analysis. The electron-withdrawing nature of these polyfluorinated phosphines was experimentally revealed via UV/vis absorption studies and crystal structure analysis. Successful catalytic application of the Au(I) complex for alkyne hydration reactions was investigated.

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. Remarkably, the photoluminescence behaviors dramatically changed during the thermal phase transition between the crystal and LC phases. Thus, these polyfluorinated bistolanes may be promising candidates for thermoresponsive luminous molecules.

Fluorine-Containing Dibenzoanthracene and Benzoperylene-Type Polycyclic Aromatic Hydrocarbons: Synthesis, Structure, and Basic Chemical Properties.

Intramolecular photocyclization of stilbene derivatives (Mallory reaction) is one of the efficient methods for building polycyclic aromatic hydrocarbon (PAH) frameworks, and is also expected to be applicable to synthesis of fluorine-containing PAHs (F-PAHs). In this study, dibenzoanthracene-type (4a) and benzoperylene-type (4b) F-PAHs were synthesized using the Mallory reaction of the 1,4-distyrylbenzene-type π-conjugated molecule (3a), which was prepared by addition-defluorination of available octafluorocyclopentene (OFCP) and aryllithium in three steps. The structure of 4a originating from π⁻π interaction was characterized by X-ray crystallographic analysis. The absorption maxima of UV-Vis spectra and emission maxima of photoluminescence spectra of the PAHs were positioned at a longer wavelength compared to those of the corresponding unsubstituted PAHs, presumably due to the electron-withdrawing nature of perfluorocyclopentene (PFCP) units. The effect of PFCP units in F-PAHs was also studied by time-dependent density functional theory (TD-DFT) calculation.

Stereochemically Defined Various Multisubstituted Alkenes Bearing a Tetrafluoroethylene (-CF2CF2-) 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.

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. It was found that dissymmetric bistolanes possess emissive features in even the LC phase and photoluminescence behaviours such as emission intensity and colour were sensitively switched depending on the molecular aggregate structure caused by applying a thermal stimulus.

Synthesis of a 1-Aryl-2,2-chlorosilyl(phospha)silene Coordinated by an N-Heterocyclic Carbene.

Phosphasilenes, P=Si doubly bonded compounds, have received considerable attention due to their unique physical and chemical properties. We report on the synthesis and structure of a chlorophosphasilene coordinated by an N-heterocyclic carbene (NHC), which has the potential of functionalization at the Si-Cl moiety. Treatment of a silylphosphine, ArPH-SiCl2RSi (Ar = bulky aryl group, RSi = Si(SiMe3)3) with two equivalents of Im-Me4 (1,3,4,5-tetramethylimidazol-2-ylidene) afforded the corresponding NHC-coordinated phosphasilene, ArP=SiClRSi(Im-Me4) as a stable compound. Bonding properties of the P=Si bond coordinated to an NHC will be discussed on the basis of theoretical calculations.

Activation of Dihydrogen by Masked Doubly Bonded Aluminum Species.

Activation of dihydrogen by masked dialumenes (Al=Al doubly bonded species) is reported. Reactions of barrelene-type dialumanes, which have the reactivity as masked equivalents of 1,2-diaryldialumenes ArAl=AlAr, with H2 afforded dihydroalumanes ArAlH2 at room temperature (Ar: bulky aryl groups). These dihydroalumanes form hydrogen-bridged dimers [ArHAl(µ-H)]2 in the crystalline state, while a monomer-dimer equilibrium was suggested in solution. The 1,2-diaryldialumenes generated from the barrelene-type dialumanes are the putative active species in the cleavage of H2 .

Ring Expansion to 1-Bromo-1-alumacyclonona-2,4,6,8-tetraene by Insertion of Two Alkyne Molecules into the Al-C Bonds.

Treatment of 1-bromo-2,3,4,5-tetraethylalumole (1) with 3-hexyne afforded the corresponding product 1-bromo-1-alumacyclonona-2,4,6,8-tetraene (2), accompanied by the formation of hexaethylbenzene. In the crystalline state, 2 forms a Br-bridged dimer with a pseudo C2-symmetric and twisted AlC8 nine-membered ring. Deuterium-labeling experiments and DFT calculations on the reaction of 1 with 3-hexyne suggested that 1-bromo-1-alumacyclohepta-2,4,6-triene, which is formed by the insertion of one molecule of 1-hexyne into the Al-C bond of alumole 1, is the key intermediate for the generation of 2 as well as hexaethylbenzene.

Reactions of diaryldibromodisilenes with N-heterocyclic carbenes: formation of formal bis-NHC adducts of silyliumylidene cations.

Reactions of stable 1,2-dibromodisilenes ((E)-Ar(Br)Si=Si(Br)Ar) with N-heterocyclic carbenes (NHC) afforded NHC-arylbromosilylene adducts or bromide salts of the corresponding bis-NHC adducts of the formal arylsilyliumylidene cations ([ArSi:](+)). In some cases, an NHC was able to replace a bromide anion in the coordination sphere of the arylbromosilylene-NHC adduct.

Syntheses and structures of terminal arylalumylene complexes.

Terminal arylalumylene complexes of platinum [Ar-Al-Pt(PCy3 )2 ] (Ar=2,6-[CH(SiMe3 )2 ]2 C6 H3 (Bbp) or 2,6-[CH(SiMe3 )2 ]2 -4-(tBu)C6 H2 (Tbb)) have been synthesized either by the reaction of a dialumene-benzene adduct with [Pt(PCy3 )2 ], or by the reduction of 1,2-dibromodialumanes Ar(Br)Al-Al(Br)Ar in the presence of [Pt(PCy3 )2 ]. X-Ray crystallographic analysis reveals that the AlPt bond lengths of these arylalumylene complexes are shorter than the previously reported shortest AlPt distance. DFT calculations suggest that the AlPt bonds in the arylalumylene complexes have a significantly high electrostatic character.

Synthesis and optical properties of antimony(V) complexes of a trianionic N2O2-type tetradentate dipyrrin ligand.

LSbCl2, an air- and moisture-stable antimony(V)-dipyrrin complex at room temperature, was obtained by treating an excess amount (20 eq.) of SbCl3 with a trianionic N2O2-type tetradentate dipyrrin ligand (L) under visible-light irradiation and O2 atmosphere. The Cl ligands in LSbCl2 were replaced by OH ligands via hydrolysis, yielding LSb(OH)2. Further, the molecular structures and optical properties of the Sb(V)-dippyrin complexes were investigated. While LSbCl2 was non-fluorescent, LSb(OH)2 exhibited an intense red fluorescence with a photoluminescence quantum yield of 68%.

Syntheses and structures of an "alumole" and its dianion.

Base free: An alumole was synthesized and treatment with lithium afforded the lithium salt of the alumole dianion. The structures of these two molecules were then investigated. The C-C bond lengths of the AlC4 ring in the dianion are nearly equal. DFT calculations revealed that the 3p(Al)-π* conjugation lowers the LUMO level of the alumole and that coordination of two lithium cations to the alumole dianion results in a planar AlC4 ring.

Synthesis of kinetically stabilized 1,2-dihydrodisilenes.

Kinetically stabilized 1,2-dihydrodisilenes were successfully synthesized and isolated by the introduction of sterically protecting bulky aryl groups. These 1,2-dihydrodisilenes exhibit distinct Si═Si double-bond character in both solution and the solid state. The Si-H bonds in these 1,2-dihydrodisilenes exhibit higher s character than those of typical σ(4),λ(4)-hydrosilanes. Moderate heating of these 1,2-dihydrodisilenes in solution resulted in their isomerization to the corresponding trihydrodisilanes, with an intramolecular hydrogen migration as the rate-determining step.

Catalytic aerobic photooxidation of triarylphosphines using dibenzo-fused 1,4-azaborines.

Although dibenzo-fused 1,4-heteroaromatics are utilized as strongly reducing photocatalysts in organic synthesis and polymerization, they have rarely been employed in catalytic photooxidation. Moreover, to date, their boron-analogs, dibenzo-fused 1,4-azaborines (DBABs), have not been applied in photocatalysis despite their promising potential as photocatalysts. Accordingly, herein, aerobic photooxidation of triarylphosphines (Ar3P) was performed using DBABs as photocatalysts. The reaction smoothly proceeded in an aprotic solvent, and phosphine oxides were obtained in appropriate yields. Density functional theory calculations suggested that DBAB captured and activated phosphadioxirane intermediates, which were generated by the interaction of Ar3P with 1O2, at the Lewis acidic boron center.