A state-averaged, multireference complete active space (CAS) approach was used for the determination of the vertical excitation energies of valence and Rydberg states of para-benzyne. Orbitals were generated with a 10- and 32-state averaged multiconfigurational self-consistent field approach. Electron correlation was included using multireference configuration interaction with singles and doubl...

Azobenzene, with two phenyl rings separated by an azo (–N=N–) bond, serves as the parent molecule for a broad class of aromatic azo compounds. These chromophores are versatile molecules, and have received much attention in research areas both fundamental and applied. The strong electronic absorption maximum can be tailored by ring substitution to fall anywhere from the ultraviolet (UV) to visib...

A negatively charged analogue of meta-benzyne, 3,5-didehydrobenzoate, was synthesized in a Fourier transform ion cyclotron resonance mass spectrometer, and its reactivity was compared to that of the same ion generated previously in a flowing afterglow apparatus and to its positively charged cousin, N-(3,5-didehydrophenyl)-3-fluoropyridinium. 3,5-Didehydrobenzoate was found to react as a nucleop...

Benzyne is shown to add elemental sulfur and give rise to a series of polysulfane compounds. A computational and experimental study is presented. Odd-membered o-C6H4Sx rings (x = 1-8), except x = 1, which suffers from ring strain, have enhanced stability compared to even-membered rings. The acquisition of "odd-even" data may shed new light, revealing patterns on polysulfane stability and struct...

Six nonlinear, optical chromophores, Z1–Z6, based on the bis(N,N-diethyl)aniline-derived donor and thiolated isophorone bridge, were designed synthesized. The was applied in a chromophore with as an electron bridge for first time. In particular, parts of chromophores Z2–Z6 modified different functional groups, including tert-butyltrimethylsilane tert-butyl(methyl)diphenylsilane derivative: 1,3-...

The arylation of bicyclic oxathiane glycosyl donors has been achieved using benzyne generated in situ from 1-aminobenzotriazole (1-ABT) and lead tetraacetate. Following sulfur arylation, glycosylation of acetate ions proceeded with high levels of stereoselectivity to afford α -glycosyl acetates in a 'one-pot' reaction, even in the presence of alternative acceptor alcohols.

Arynes continue to stimulate new reactions and theoretical insight in aromatic chemistry. This has been driven in recent years by the exceptional versatility of 2-(trimethylsilyl)phenyl triflate (1) as a precursor to ortho-benzyne. Such compounds react under mild conditions and have enabled a substantial development of aryne chemistry both in terms of classical transformations (nucleophilic add...

Recently, individual single-walled carbon nanotubes (SWNTs) functionalized with azo-benzene chromophores were shown to form a new class of hybrid nanomaterials for optoelectronics applications. Here we use a number of experimental and computational techniques to understand the binding, orientation, and nature of coupling between chromophores and the nanotubes, all of which are relevant to futur...

A facile approach for the covalent functionalization of carbon nanohorns (CNHs) based on the benzyne cycloaddition reaction is presented. The benzynes were in situ generated from either anthranilic acid by decomposition of the internal benzenediazonium-2-carboxylate or from 2-(trimethylsilyl)-phenyl triflate by fluoride ion attack at the silicon atom followed by displacement of the trimethylsil...