Oxidative Organic Transformations Photocatalyzed by NDI in Visible Light.

In this work, we report the synthesis and photocatalytic properties of -bis(-hexyl)-2-bromo-6-(-hexylamino)-1,4,5,8-naphthalenetetracarboxylic diimide photocatalyst, , in visible light. In the presence of air or oxidant, efficiently enables multiple photooxygenations of isoquinolines, thiocyanation of phenylimidazopyridines, functionalization of quinolinones by allowing regioselective installation of an SCN, SeCN, SPh, SePh, Cl, Br, or I group at the C-3 position, and isomerization of alkenes. Mechanistic investigations suggest an oxidative photoredox process for oxygenation and C-H functionalization, while isomerization is believed to proceed through a photosensitization pathway.

Bronsted Acid-Catalyzed Regioselective Carboxamidation of 2-Indolylmethanols with Isonitriles.

A regioselective direct carboxamidation reaction of 2-indolylmethanols with readily available isocyanoesters/isocyanides has been reported in this work. The reaction was catalyzed by Bronsted acid such as -TsOH to deliver the benzylic regioselective amides in 67-86% yield under mild conditions. The developed methodology provides alternative access to traditional metal-free carboxamidation via C-C and C-O bond formation with high atom economy.

Synthesis and Properties of Electron-Deficient and Electron-Rich Redox-Active Ionic π-Systems.

There is growing interest towards the design and synthesis of organic redox-active systems, which exist in ionic form. Multi- redox systems entail life-sustaining processes like photosynthesis and cellular respiration. The significant challenge for material scientists is to rationally design complex molecular materials that can store and transfer multiple electrons at low operational potentials and are stable under ambient conditions.

Synthesis of a Highly Electron-Deficient, Water-Stable, Large Ionic Box: Multielectron Accumulation and Proton Conductivity.

π-acidic boxes exhibiting electron reservoir and proton conduction are unprecedented because of their instability in water. We present the synthesis of one of the strongest electron-deficient ionic boxes showing e uptake as well as proton conductivity. Two large anions fit in the box to form anion-π interactions and form infinite anion-solvent wires.

Appending Diverse π-Extended Acceptors with Tetrathiafulvalene/Dithiafulvalene Donors: Multistate Redox Properties, Radical Ion Generation, and Mid-IR-Absorbing Mixed-Valence States.

Three classes of donor-acceptor (D-A) π-extended chromophores (1-12) were synthesized through a phosphite-mediated cross-coupling reaction, in which the anhydride- or imide-based π-As and number of tetrathiafulvalene (TTF)/dithiafulvalene (DTF) Ds were systematically changed. Large π rings, such as benzoperylene and coronene, were integrated into the TTF/DTF unit, for the first time, to overcome their high insolubility. The anhydride and imide groups in the π acceptors can significantly alter the frontier orbitals and influence the optoelectronic properties.