Red/NIR-Emissive Benzo[d]imidazole-Cored AIEgens: Facile Molecular Design for Wavelength Extending and In Vivo Tumor Metabolic Imaging.

Aggregation-induced emission (AIE) luminogens (AIEgens) with red/near-infrared (NIR) emissions are appealing for applications in optoelectronics and biomedical engineering owing to their intrinsic advantages of efficient solid-state emission, low background, and deep tissue penetration. In this context, an AIEgen with long-wavelength emission is synthesized by introducing tetraphenylethene (TPE) to the periphery of electron-deficient spiro-benzo[d]imidazole-2,1'-cyclohexane (BI). The resulting AIEgen, abbreviated as 2TPE-BI, adopts a donor-acceptor structure and shows bathochromic absorption and emission with a larger Stokes shift of 157 nm in acetonitrile than that based on benzo[c][1,2,5]thiadiazole. It also exhibits a high solid-state fluorescence quantum yield of 56.6%. By further insertion of thiophene to its molecular structure generates 2TPE-2T-BI with higher conjugation and NIR emission. 2TPE-2T-BI can be fabricated into AIE dots for in vivo metabolic labeling through bio-orthogonal click chemistry. These results open a new approach for facile construction of long-wavelength emissive AIEgens based on the BI core.