Tuning the Optical Properties of Sulfonylaniline Derivatives: Degeneracy Breaking of Benzene Orbitals and Linkage through Nodal Planes.

The orbital degeneracy of benzene rings is resolved by an asymmetric push-pull system in 2,6-bis(methylsulfonyl)aniline (BMeSA), in which the highest occupied molecular orbital (HOMO) is located at the 4-position, while the lowest unoccupied molecular orbital (LUMO) is located at a different position and has a nodal plane through the carbon atoms at the 1- and 4-positions. Therefore, the π-extension of BMeSA at the 4-position reveals a strong overlap in the HOMO and a minimal overlap in the LUMO. Consequently, π-extended BMeSA derivatives exhibit longer absorbance and emission wavelengths in the order of the electron-donating abilities of their substituents at the 4-position, which is based on a decrease in an absolute HOMO-level-dependent HOMO-LUMO gap in accordance with the nodal arrangement. Positive fluorescent solvatochromism with polarity-dependent decrease in fluorescent intensity was also observed. The biaryls exhibited more planar geometries in the excited state than in the ground state. The charge transfer mechanism, which can be described as node-induced intramolecular charge transfer (NICT), differs from the planar intramolecular charge transfer (PICT) and twisted intramolecular charge transfer (TICT).

Direct Silyl-Heck Reaction of Chlorosilanes.

A nickel complex/Lewis acid combination effectively catalyzed the direct silyl-Heck reaction of chlorosilanes, which are key raw materials in the organosilicon industry, to give synthetically important alkenylsilane products. Trichlorosilanes, dichlorosilanes, and monochlorosilanes underwent the silyl-Heck reaction to afford the corresponding alkenylsilanes in high yields. In the reactions of dichlorosilanes, a single substitution occurred to give monoalkenylsilanes in a highly selective manner.

Singlet Fission of Non-polycyclic Aromatic Molecules in Organic Photovoltaics.

Singlet fission of thienoquinoid compounds in organic photovoltaics is demonstrated. The escalation of the thienoquinoid length of the compounds realizes a suitable packing structure and energy levels for singlet fission. The magnetic-field dependence of the photocurrent and the external quantum efficiency of the devices reveal singlet fission of the compounds and dissociation of triplet excitons into charges.

Single Benzene Green Fluorophore: Solid-State Emissive, Water-Soluble, and Solvent- and pH-Independent Fluorescence with Large Stokes Shifts.

Benzene is the simplest aromatic hydrocarbon with a six-membered ring. It is one of the most basic structural units for the construction of π conjugated systems, which are widely used as fluorescent dyes and other luminescent materials for imaging applications and displays because of their enhanced spectroscopic signal. Presented herein is 2,5-bis(methylsulfonyl)-1,4-diaminobenzene as a novel architecture for green fluorophores, established based on an effective push-pull system supported by intramolecular hydrogen bonding. This compound demonstrates high fluorescence emission and photostability and is solid-state emissive, water-soluble, and solvent- and pH-independent with quantum yields of Φ=0.67 and Stokes shift of 140 nm (in water). This architecture is a significant departure from conventional extended π-conjugated systems based on a flat and rigid molecular design and provides a minimum requirement for green fluorophores comprising a single benzene ring.

2,6-Bis(arylsulfonyl)anilines as Fluorescent Scaffolds through Intramolecular Hydrogen Bonds: Solid-State Fluorescence Materials and Turn-On-Type Probes Based on Aggregation-Induced Emission.

A series of 2,6-bis[aryl(alkyl)sulfonyl]anilines were synthesized by nucleophilic aromatic substitution of 2,6-dichloronitrobenzene with various aryl or alkyl thiolates (benzyl-, phenyl-, 2-naphthyl-, and 2-aminophenyl thiolate), followed by hydrogenation and subsequent oxidation. All prepared 2,6-bis[aryl-(alkyl)sulfonyl]anilines showed high fluorescence emissions in the solid state; X-ray structures revealed well-defined intramolecular hydrogen bonds, which served to immobilize the rotatable amino group and generate a fluorescence enhancement in addition to improved photostability. Moreover, absorption and fluorescence spectra showed redshifts in the order of benzyl