One-Shot Double Amination of Sondheimer-Wong Diynes: Synthesis of Photoluminescent Dinaphthopentalenes.

Photoluminescent diamino-substituted dinaphthopentalenes were synthesized successfully by the treatment of in situ prepared dinaphthocyclooctadiyne with lithium amide. This reaction involves a series of transformations including the nucleophilic addition of the lithium amide to a triple bond of the cyclooctadiyne moiety, transannulation, protonation of the resulting pentalene anion, and the nucleophilic substitution of the pentalene core with the lithium amide. In this procedure, a novel double amination step plays a key role. When the diamino-substituted dinaphthopentalenes were irradiated with UV light in toluene, fluorescence was observed at around 580 nm (ΦF < 0.03).

Extended halogen bonding between fully fluorinated aromatic molecules.

Halogen bonding is a noncovalent interaction where an electrophilic cap on a halogen atom, the so-called σ-hole, attracts a nucleophilic site on an adjacent molecule. The polarizability of halogens relates to the strength of the σ-hole, and accordingly the halogen-halogen distance becomes shorter in the order of Cl, Br, and I. Fully fluoro-substituted aromatic molecules, on the contrary, are generally believed not to form halogen bonds due to the absence of a σ-hole. Here, we study atomic-scale in-plane F-F contacts with high-resolution force microscopy. Our ab initio calculations show that the attractive dispersion forces can overcome the electrostatic repulsion between the fluorine atoms, while the anisotropic distribution of the negative electrostatic potential leads the directional bond and even changes the gap. The coexistence of these two competing forces results in the formation of a "windmill" structure, containing three C-F···F bonds among neighboring molecules. While the σ-hole is absent, the scheme of the C-F···F bonding has a high similarity to halogen bonding.

Substituted 5,6,11,12-tetradehydrodibenzo[a,e]cyclooctenes: syntheses, properties, and DFT studies of substituted Sondheimer-Wong diynes.

Highly strained cyclic acetylenes 5,6,11,12-tetradehydrodibenzo[a,e]cyclooctenes (Sondheimer-Wong diynes) having various substituents on their benzene rings were synthesized successfully by one-pot treatment of the corresponding formyl sulfones with diethyl chlorophosphate/lithium hexamethyldisilazide (LiHMDS) and then lithium diisopropylamide (LDA). When mixtures of two types of formyl sulfones bearing different substituents were subjected to this protocol, the unsymmetrically substituted Sondheimer-Wong diynes could be synthesized in a stepwise manner by isolation of the heterocoupled vinyl sulfone intermediates followed by their treatment with LDA. The UV-vis absorption spectra and cyclic voltammograms of the substituted Sondheimer-Wong diynes were recorded. The electronic effect of substituents on the diynes was investigated in their click reactions and nucleophilic and electrophilic additions.

Image distortions of a partially fluorinated hydrocarbon molecule in atomic force microscopy with carbon monoxide terminated tips.

The underlying mechanisms of image distortions in atomic force microscopy (AFM) with CO-terminated tips are identified and studied in detail. AFM measurements of a partially fluorinated hydrocarbon molecule recorded with a CO-terminated tip are compared with state-of-the-art ab initio calculations. The hydrogenated and fluorinated carbon rings in the molecule appear different in size, which primarily originates from the different extents of their π-electrons. Further, tilting of the CO at the tip, induced by van der Waals forces, enlarges the apparent size of parts of the molecule by up to 50%. Moreover, the CO tilting in response to local Pauli repulsion causes a significant sharpening of the molecule bonds in AFM imaging.

One-pot transformation of Ph2P(O)-protected ethynes: deprotection followed by transition metal-catalyzed coupling.

Ph2P(O)-protected ethynes were successfully transformed to arylethynes in one-pot manner through t-BuOK-catalyzed deprotection followed by Sonogashira coupling with aryl halide. The arylethynes were obtained similarly by Ph2P(O)-deprotection, stannylation of the resulting terminal ethynes, and Migita-Kosugi-Stille coupling. Deprotection followed by intramolecular Eglinton coupling could be carried out in one-pot to provide cyclic butadiynes.

Obtaining detailed structural information about supramolecular systems on surfaces by combining high-resolution force microscopy with ab initio calculations.

State-of-the art experimental techniques such as scanning tunneling microscopy have great difficulties in extracting detailed structural information about molecules adsorbed on surfaces. By combining atomic force microscopy and Kelvin probe force microscopy with ab initio calculations, we demonstrate that we can obtain a wealth of detailed structural information about the molecule itself and its environment. Studying an FFPB molecule on a gold surface, we are able to determine its exact location on the surface, the nature of its bonding properties with neighboring molecules that lead to the growth of one-dimensional strips, and the internal torsions and bendings of the molecule.

Photoinduced charge-transfer dynamics of sequentially aligned donor-acceptor systems in an ionic liquid.

Photoinduced charge separation processes of linear phenyleneethynylene derivatives (PEN) with different sequences of electron-withdrawing perfluorophenyl groups (A) and electron-donating phenyl groups (D) were investigated in an ionic liquid (IL), BmimTFSI, by picosecond time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopies. Very rapid photoinduced charge separation within 10 ps in AADD was followed by the stabilization of the charge-transfer (CT) state by the solvation, while the excited states in ADAD and ADDA were ascribable to the locally excited (LE) state. Equilibrium between the LE and CT states was established for DAAD with time constants of forward and backward processes much faster than the solvation time. The relative population of the CT state increases with time owing to the dynamic stabilization of the CT state by the solvation. The elementary charge separation process, the increase in the CT population, and their relation to the solvation time were discussed.

Dihalo-substituted dibenzopentalenes: their practical synthesis and transformation to dibenzopentalene derivatives.

Diiodo- and bromo, iodo-substituted dibenzopentalenes were obtained by treatment of 5,6,11,12-tetradehydrodibenzo[a,e]cyclooctene with I(2) and IBr, respectively. These dihalo-substituted pentalenes reacted with terminal ethynes in Sonogashira coupling and with arylboronic acid in Suzuki-Miyaura coupling to give a series of phenylethynyl- and/or aryl-substituted pentalenes. Suzuki-Miyaura coupling of the halopentalenes with in situ prepared pentaleneboronic esters provided bis-, tri-, and tetra(dibenzopentalene)s. It was found that these dibenzopentalene oligomers underwent facile electrochemical reduction and exhibited a bathochromic shift in UV-vis absorption spectra because of their expanded π-systems.

Enantiopure double-helical phenylene ethynylene cyclophynes with the 2,2'-binaphthyl template.

New types of enantiopure compounds were synthesized to gain better insight into the structural features of phenylene ethynylene cyclophynes. Besides the previously obtained meta-substituted arylene ethynylenes, 1, ortho-connected phenylene ethynylene units were incorporated to give cyclophynes with ortho/meta and ortho/ortho connection modes, 2 and 3. Furthermore, a diphenylethyne component was also accommodated in 4. Both ab initio calculations and NMR spectra suggest a large amount of strain for 2 but less strain for 3 and 1 a, the latter having the smallest ring size among cyclophynes with the meta/meta connection mode. The CD spectra of 2 and 3 showed a characteristic shoulder at around 340 nm, similar to the case of 1 a. This implies that the aromatic acetylene bonds cross over each other in the double-helical structure. These results indicate that chirality information is useful for probing the persistency of molecular shape.

Electrical properties of 1,4-bis(4-(phenylethynyl)phenylethynyl)benzene and its application for organic light emitting diodes.

We found that a phenylene ethynylene derivative, 1,4-bis(4-(phenylethynyl)phenylethynyl)benzene (BPPB), provides very high photoluminescence efficiency both in solution (Phi(PL) = 95 +/- 3%) and thin films (Phi(PL) = 71 +/- 3%); further, we observed blue electroluminescence (EL) of lambda(EL(max)) approximately 470 and 510 nm with an external EL efficiency of eta(EL) approximately 0.53% and maximum luminance of approximately 70000 cd m(-2) at current density of approximately 2 A cm(-2) with BPPB as an emitter; also we identified that BPPB functions as a hole transport layer in organic light emitting diodes.

Synthesis and spectroscopic studies of arylethynylsilanes.

A variety of arylethynylsilanes (Ar-C[triple bond]C-C6H4-C[triple bond]C)(n)SiMe(4-n) were prepared successfully by reaction of the corresponding chlorosilanes Me(4-n)SiCl(n) with Ar-C[triple bond]C-C6H4-C[triple bond]CM (M = Li, MgBr), which was prepared by treatment of ethynyl(diarylethyne)s Ar-C[triple bond]C-C6H4-C[triple bond]CH with BuLi or MeMgBr. The ethynyl(diarylethyne)s were readily prepared in good yields by the double-elimination method: addition of lithium hexamethyldisilazide to a mixture of ArCH2SO2Ph, TMS-C[triple bond]C-C6H4-CHO, and ClP(O)(OEt)2, followed by desilylation. In the tetrakis(arylethynyl)silanes (Ar-C[triple bond]C-C6H4-C[triple bond]C)4Si thus prepared, through-space conjugation of four triple bonds on the silicon atom emerges as a result of participation of the silicon orbitals in the acetylenic pi orbitals. This participation enhances the emissive quantum yields of arylethynylsilanes with an increase in the number of arylethynyl moieties on silicon: quantum yields of emission (phiF) of 0.72 for (MeOC6H4-C[triple bond]C-C6H4-C[triple bond]C)4Si, 0.53 for (MeOC6H4-C[triple bond]C-C6H4-C[triple bond]C)2SiMe2, and 0.47 for MeO-C6H4-C[triple bond]C-C6H4-C[triple bond]CSiMe3 were obtained. Although this enhancement effect was also observed in the phenylethynylarylsilane (MeOC6H4-C[triple bond]C-C6H4)2SiMe2, the bis(arylethynyl)disilane (MeOC6H4-C[triple bond]C-C6H4-C[triple bond]C-SiMe2)2 exhibited non-enhanced emission.

Rate acceleration of organic reaction by immediate solvent evaporation.

Several types of organic reactions were accelerated by immediate evaporation of solvents because of remarkable enhancement of molecule-to-molecule contacts between reactants.

Fluorophilicity switch by solvation.

A new type of fluorous distannoxanes, [XRf2SnOSnRf2Y]2 (Rf = C6F13C2H4; X, Y = C6F13SO3 (2) and (C6F13SO2)2N, Cl (3)) was prepared successfully as hydrates from the reaction of [ClRf2SnOSnRf2Cl]2 with C6F13SO3Ag and (C6F13SO2)2NAg, respectively. Despite their high fluorine content (59.85 and 59.27% F), these distannoxanes were completely insoluble in fluorocarbons as well as hydrocarbons and halo alkanes. In contrast to this, fluorous distannoxanes 2 and 3 were soluble in polar organic solvents, such as EtOAc, acetone, and THF. When 2 and 3 were added to a two-phase mixture of fluorocarbon and EtOAc, the mixture turned miscible in proportion to the amount of 2 and 3 added, and finally, the mixture turned to a homogeneous solution.

Organotin perfluorooctanesulfonates as air-stable Lewis acid catalysts: synthesis, characterization, and catalysis.

The reactions of 1,3-dichloro-1,1,3,3-tetrabutyldistannoxane and dialkyltin dihalides with silver perfluorooctanesulfonate provided the corresponding sulfonates as hydrates. The number of water molecules (n) of hydration was dependent on the conditions. The distannoxane derivative was identified as n from 0.5 to 6, while in the hydrated mononuclear species and DMSO complexes n varied widely from 4 to 13. 119Sn NMR spectroscopy and conductivity measurements indicated the ionic dissociation of these compounds in solution. These compounds exhibited unusually high solubility in polar organic solvents. The ionic dissociation together with facile hydration probably causes the unusual solubility. The Lewis acidity of these compounds was found to be high among organotin derivatives on the basis of ESR spectra of superoxide/metal-ion complexes. In contrast to well-known organotin triflates, these compounds suffered no hydrolysis upon storage in open air. The high catalytic activity of the distannoxane 1 was exemplified for various carbon-carbon bond-forming reactions, such as Mukaiyama-aldol as well as -Michael reactions and allylation of aldehydes.

One-shot double elimination process: a practical and concise protocol for diaryl acetylenes.

A variety of diaryl acetylenes were obtained in good yields when lithium hexamethyldisilazide was added to a solution of arylmethyl sulfone, aryl aldehyde, and chlorodiethylphosphate in THF. In this one-shot process, a number of transformations such as aldol reaction, phosphorylation of aldolate, and double elimination of the resulting beta-substituted sulfone proceeded successively to afford the desired acetylenes. The one-shot process was accelerated by the substitution of halogen atoms on the phenyl groups, and unsymmetrically substituted diaryl acetylenes were obtained without contamination of the dehalogenated products. Diaryl acetylenes with other substituents such as CF3, ethoxycarbonyl, dimethylamino, TMS-acetylene groups, as well as pyridinyl and thienyl moieties were also accessible with this method. However, methoxy-substituted compounds were obtained in moderate yields under the same conditions, but the yields were increased when lithium diisopropylamide was used instead.

Novel synthesis of 2-aryl and 2,3-disubstituted indoles by modified double elimination protocol.

[reaction: see text] Syntheses of 2-aryl and 2,3-substituted indoles were realized by modified double elimination protocol. Under basic conditions, vinyl sulfones derived from the reaction of 2-aminobenzyl sulfone with benzaldehydes underwent cyclization and alkylation followed by elimination of sulfinic acid to afford 2,3-substituted indoles.

Synthesis and properties of 1,6,7,12,13,18,19,24-octamethylacenaphthyleno[b,l]tetraphenylene.

The X-ray crystal structure and photophysical properties of 1,6,7,12,13,18,19,24-octamethylacenaphthyleno[b,l]tetraphenylene, which has been synthesized via a Diels-Alder reaction of 5,6,11,12-tetradehydrodibenzo[a,e]cyclooctene and 6,7-dihydro-6-hydroxy-7,9-dimethyl-8H-cyclopenta[a]acenaphthylene-8-one, are reported.

Metal-assisted assembly of pyridine-containing arylene ethynylene strands to enantiopure double helicates.

Pyridine-containing arylene ethynylene strands were connected to the 2- and 2'-positions of (R)- and (S)-1,1'-binaphthyl templates. The arylene ethynylene moieties underwent intramolecular coordination with Ag(I) or Cu(I) ion to afford enantiopure double helicates. The double-helical structure was elucidated on the basis of circular dichroic (CD) spectra. The importance of intramolecular complexation of the double strands for the helicate formation was confirmed by comparison with a ligand bearing a single strand. Connection of the strands through an ether linkage enabled a sorting out of the Cotton effect induced by double-helical arylene ethynylene moieties. The CD exciton chirality method unambiguously proved that the termini of the strands approach each other upon complexation and that the sense of the induced helicity is the same as predicted by molecular modeling.