Molecules with intense near‐IR (NIR) emission are beneficial for modern applications such as night vision, bio‐imaging etc. However, elaborate synthetic manipulations make them demanding to accomplish. Herein, we present a simple yet exciting strategy to obtain novel Janus butterfly‐shaped terrylene diimide derivatives with carbazole wings having absorption and intense emission in the NIR. Especially, unsymmetrically substituted terrylene diimides (TDIs) have been observed to have impressive emission quantum yields (up to 93 %), highest for this class of compounds. Minimal structural distortion as evidenced from structural characterization has been shown to correlate with these observations. Also, a novel two‐tiered TDI‐carbazole having an intense emission at 897 nm is also reported. Our strategy demonstrates that efficient near‐IR luminophores can be achieved via precise functionalization.

Herein, we present the first examples of air-stable, deep-lowest unoccupied molecular orbital (LUMO) polycyclic aromatic molecules with emission in the near-infrared (NIR) region, using nitration as a strategy. Despite the...

Diverse applications of rylenediimides are attributed to the accessibility of simple methodologies to obtain versatile halogenated precursors. Terrylene diimides are important molecular platforms to achieve materials with NIR absorption and emission. In this work, we present a simple synthesis for the hitherto unknown di- and tribromo-TDIs. Regioisomerically pure dibromo TDIs, including an elusive 1,14-derivative, could be successfully isolated and structurally characterized along with tribromo-TDI. The utility of these bromo derivatives has also been demonstrated with a redox anchoring.

Three new symmetrically para‐phenylethynylene‐substituted terrylene diimide derivatives namely, TDI‐Ph, TDI‐PhCN and TDI‐PhNMe2 were synthesized to study the electronic effects on the structure and properties. The solid‐state single‐crystal structures for TDI‐Ph and TDI‐PhCN as well as for the precursor TDI‐Br4 are presented. The X‐ray diffraction studies revealed twisting in the bay‐area of terrylene core, which improved the solubility as well, despite of having some of the shortest intermolecular Br···Br and C‐H···O interactions in TDI‐Br4. All the compounds exhibited near infra‐red absorption and emission except for TDI‐PhNMe2; especially TDI‐PhNMe2 showed interesting broad absorption ranging from 300 to 970 nm. Further, the effects of electron‐donating and accepting unit on electrochemical and optical properties have been investigated.

Molecules with intense near‐IR (NIR) emission are beneficial for modern applications such as night vision, bio‐imaging etc. However, elaborate synthetic manipulations make them demanding to accomplish. Herein, we present a simple yet exciting strategy to obtain novel Janus butterfly‐shaped terrylene diimide derivatives with carbazole wings having absorption and intense emission in the NIR. Especially, unsymmetrically substituted terrylene diimides (TDIs) have been observed to have impressive emission quantum yields (up to 93 %), highest for this class of compounds. Minimal structural distortion as evidenced from structural characterization has been shown to correlate with these observations. Also, a novel two‐tiered TDI‐carbazole having an intense emission at 897 nm is also reported. Our strategy demonstrates that efficient near‐IR luminophores can be achieved via precise functionalization.