Synthesis, structures, and solid-state photoresponsive color change behavior of boronium complexes bearing a pyridine-imine, diimine, or pyridine-ketone bidentate ligand.

9-Borabicyclo[3.3.1]nonane-based boronium triflates bearing a N-substituted 2-pyridylmethanimine, N,N'-dialkylethane-1,2-diimine, or 2-arylcarbonylpyridine ligand were synthesized. Their tetracoordinate boron structures were determined using 11B NMR spectra and X-ray crystallography. The pyridine-imine complexes exhibited solid-state photoresponsive color changes upon UV irradiation, which indicated that boronium complexes without a bipyridine moiety also have photoresponsive capabilities. Combination of TD-DFT calculations and measurements of UV-vis absorption and fluorescence properties, diffuse reflectance spectra, and ESR spectra provided suggestions on the determining factor of the photoresponsive color change capabilities and structures of the photoproducts.

Effects of π-conjugation on the solid-state photoresponsive coloring behavior of bipyridine-boronium complexes.

Solid-state photoinduced coloring of boronium complexes consisting of 9-borabicyclononane and 2,2'-bipyridine with π-conjugated substituents at the 4,4'- or 5,5'-positions was investigated. The substitution position affected the highest occupied molecular orbital distribution and determined the coloring capability. The 4,4'-substituted complexes exhibited coloration upon irradiation, whereas most of the 5,5'-substituted complexes did not.

Fluorescent azobenzenes and aromatic aldimines featuring an N-B interaction.

Azobenzenes are constituents of the commonly and widely used azo dyes. Many dyes, except for the azo dyes, have been utilized for fluorescent materials. However, there are only a few fluorescent azobenzene derivatives and their fluorescence efficiencies are quite low. The current perspective provides an account of the fluorescent azobenzenes and aromatic aldimines featuring an N-B interaction. Incorporation of the intramolecular N-B interaction by using the bis(pentafluorophenyl)boryl group makes the azobenzenes and aromatic aldimines fluorescent with a range of colours. Some of them fluoresce with extraordinarily high fluorescence quantum yields. Their synthesis, structures, fluorescence properties, and applications are discussed.

Elongation of phenoxide C-O bonds due to formation of multifold hydrogen bonds: statistical, experimental, and theoretical studies.

Statistical studies using the Cambridge Structural Database have revealed that there are several elongated phenoxide C-O bonds. They are characterized by the formation of 3-fold (or occasionally 2-fold) hydrogen bonds to the phenoxide oxygen atoms, and their mean bond length extends up to 1.320 Å, which is quite different from the theoretically predicted carbon-oxygen bond length of C(6)H(5)O(-) (1.26 Å). Elongated phenoxide C-O bonds associated with the formation of 3-fold hydrogen bonds were also observed in the X-ray structures of proton-transfer complexes (2X-O(-))(TEAH(+))s derived from 5'-X-substituted 5,5''-dimethyl-1,1':3',1''-terphenyl-2,2',2''-triols (2X-OHs, where X = NO(2), CN, COOCH(3), Cl, F, H, and CH(3)) and triethylamine (TEA). By comparing the X-ray structures, C-O bond elongation was found to be only slightly affected by an electron-withdrawing substituent at the para position (X). This along with strong bathochromic shifts of N-H(···O(-)) and O-H(···O(-)) stretching vibrations in the IR spectra indicates that the elongated C-O bonds in (2X-O(-))(TEAH(+))s essentially have single-bond character. This is further confirmed by molecular orbital calculations on a model complex, showing that the negatively charged phenoxide oxygen atom is no longer conjugated to the central benzene ring, and the NICS values of the three benzene rings are virtually identical. However, C-O bond elongation in (2X-O(-))(TEAH(+))s was considerably influenced by a change in the hydrogen-bond geometry. This also suggests that hydrogen bonds significantly affect phenoxide C-O bond elongation.

Intensely fluorescent azobenzenes: synthesis, crystal structures, effects of substituents, and application to fluorescent vital stain.

2-[Bis(pentafluorophenyl)boryl]azobenzenes bearing hydrogen, methoxy, dimethylamino, trifluoromethyl, fluoro, n-butyl, and tert-butyldimethylsiloxy groups at the 4'-position or methoxy and bromo groups at the 4-position have been synthesized. The 4-bromo group of the 2-boryl-4-bromoazobenzene derivative was converted to phenyl and diphenylamino groups by palladium-catalyzed reactions. The absorption and fluorescence properties have been investigated using UV/Vis and fluorescence spectroscopy. The 2-borylazobenzenes emitted an intense green, yellow, and orange fluorescence, in marked contrast to the usual azobenzene fluorescence. The 4'-siloxy derivative showed the highest fluorescence quantum yield (0.90) among those reported for azobenzenes to date. The correlation between the substituent and the fluorescence properties was elucidated by studying the effect of the substituent on the relaxation process and from DFT and TD-DFT calculations. An electron-donating group at the 4'-position was found to be important for an intense emission. Application of fluorescent azobenzenes as a fluorescent vital stain for the visualization of living tissues was also investigated by microinjection into Xenopus embryos, suggesting these compounds are nontoxic towards embryos.

Fluorescence properties of simple N-substituted aldimines with a B-N interaction and their fluorescence quenching by a cyanide ion.

N-Aryl, N-alkyl, N-alkoxy, and N-amino derivatives of 2-[bis(pentafluorophenyl)boryl]benzylideneamine were synthesized by the condensation reactions of 2-[bis(pentafluorophenyl)boryl]benzaldehyde with the corresponding amines. Their structures were investigated by NMR and X-ray crystallographic analysis. Their properties were investigated by UV-vis and fluorescence spectroscopy. The boryl-substituted N-arylimines show blue or green fluorescence in hexane at room temperature, and their fluorescence efficiency is much higher than that of N-benzylideneaniline. In particular, the boryl-substituted N-(4-dimethylaminophenyl)imine showed strong green emissions with at least 7000 times higher fluorescence quantum yield (0.73) compared with that of N-benzylideneaniline. The boryl-substituted N-(1-indolyl)- and N-(9-carbazolyl)imines showed dual emissions, one of which was assignable as arising from the lowest singlet excited state and the other from the local excited state of the substituent on the imine nitrogen. The fluorescent properties of the boryl-substituted N-butyl- and N-methoxyimines were also investigated. Reactions of the N-arylimine derivatives with cyanide ion gave the corresponding cyanide adducts and quenched the fluorescence, indicating that these 2-[bis(pentafluorophenyl)boryl]benzylideneamine derivatives have a potential as a cyanide ion sensor.

Synthesis of the most intensely fluorescent azobenzene by utilizing the B-N interaction.

A boron-substituted azobenzene, (E)-[2-(4-methoxyphenylazo)phenyl]bis(pentafluorophenyl)borane, presented the most intense fluorescence among the azobenzene derivatives.

Photoswitching of the Lewis acidity of a catecholborane bearing an azo group based on the change in coordination number of boron.

Photoisomerization of a catecholborane bearing a 2-(phenylazo)phenyl group with an N-B dative bond caused photoswitching of the coordination number of boron between 3 and 4. The Lewis acidity of the catecholborane was switched by photoirradiation, and the complexation ability of the (E)- and the (Z)-isomers of the catecholborane with pyridine differs by more than a factor of 300. [reaction: see text]