Non-alternant Benzodifluoranthene Tetraimides from 7,8,9,10-Fluoranthene Diimides: Synthesis, Structure, and Optical-Limiting Properties.

Abstract

A novel tetraimide-functionalized non-alternant π-conjugated system, namely, benzodifluoranthene tetraimides (BDFTI), has been designed and synthesized through highly efficient UV-photocyclization of a vinyl-bridged fluoranthene diimide dimer (i. e., FDI-V). The synthesis of FDI-V starts from a straightforward three-step route to produce novel 7,8,9,10-fluoranthene diimide (FDIs) building-blocks, followed by nearly complete bromination and then Stille-coupling reaction to give the desired dimer. The analysis by X-ray crystallography confirms a near-coplanar geometry for FDIs, while BDFTI shows a U-shaped and distorted backbone configuration proven by theoretical optimizations. The tetraimide BDFTI exhibits several advantages over the FDI cores, including an extended absorption band and a red-shift in photoluminescence spectra. This enhancement can be attributed to the presence of additional electron-deficient imide units, which promotes increased intramolecular charge transfer and improved electron affinity. All the imides show a local aromatic characteristic owing to the incorporation of pentagon rings in the π-frameworks. The fully fused BDFTI exhibits nonlinear optical properties as analyzed by the open-aperture Z-scan technique, demonstrating superior optical-limiting performance compared to vinyl-bridged FDI-V. The versatile UV-photocyclization chemistries provide a pathway for developing complex and unique multiimide-functionalized π-conjugated systems, paving the way for creating high-performance optical-limiting materials.