Annulated oxazolium anion-π AIEgens.

A new class of anion-π AIEgens based on ring-fused annulated oxazolium architectures is reported, which can be readily synthesized a single-step dual C-H activation annulative π-extension (APEX) protocol from simple oxazolium salts. The crucial and decisive role of anion-π interactions in their solid-state structural arrangement was analyzed to correlate their tunable AIE features and solid-state quantum yields.

Orchestrated Octuple C-H Activation: A Bottom-Up Topology Engineering Approach toward Stimuli-Responsive Double-Heptagon-Embedded Wavy Polycyclic Heteroaromatics.

Curiosity-driven innovations on the design and synthesis of nonplanar polycyclic aromatic/heteroaromatic compounds with new molecular topologies unfold exciting opportunities for harnessing their intriguing supramolecular properties and thereby the development of novel functional organic materials. This work presents such an innovative synthetic concept of a bottom-up molecular topology engineering through a unique orchestrated octuple C-H activation reaction, toward the rapid synthesis of a novel class of double heptagon-incorporated nitrogen-doped laterally-fused polycyclic compounds with rarely reported wavy structural configuration. The profound impact of the molecular wavy structures of these compounds on their properties is manifested by weak and tunable solid-state intermolecular interactions controlling the electronic properties of the materials, leading to reversibly switchable fluorochromism in the solid state and thin films with mechanical force and solvent vapors as external stimuli, thereby indicating their potential applicability in rewritable fluorescent optical recording media, security papers, mechanosensors, volatile organic compound (VOC) sensors etc.

Unveiling N-Fused Nitreniums as Potent Catalytic Photooxidants.

The first example of a hitherto-unknown facet of catalytic photooxidant capability of nitrenium cations is reported herein. The fundamental limitation of inability of the traditional and reported nitreniums to achieve the excited-state redox potential beyond +2.0 V (vs Ag/AgCl), the primary requirement for a powerful photooxidant, is addressed in this work by developing a structurally unique class of N-fused nitrenium cations, with the required structural engineering involving extensive π-conjugation through ring fusion at the nitrenium site, which enabled significant lowering of the LUMO energy and easy reduction at the excited state (excited-state redox potential up to +2.

Cationic π-extended heteroaromatics a catalytic C-H activation annulative alkyne-insertion sequence.

Cationic π-conjugated organic molecules have broad applications in materials science as next-generation organic materials. The annulative alkyne-insertion π-extension (AAIPEX) strategy has emerged as a promising synthetic approach for the rapid synthesis of cationic polycyclic heteroaromatic compounds (cPHACs) in a single step. The AAIPEX reaction provides a synthetic shortcut to achieve complex organic molecules from simple (hetero)arene templates and alkynes as π-extending partners, which would otherwise be difficult to achieve using traditional methods.