Activatable near‐infrared (NIR) dyes responsive to external stimuli are used in medical and other applications. Here, we describe the design and synthesis of bench‐stable 18π‐ and 20π‐electron benzitetraazaporphyrins (BzTAPs) possessing redox‐switchable NIR properties. X‐Ray, NMR, and UV/Visible‐NIR analyses revealed that 20π‐electron BzTAP 1 exhibits NIR absorption and antiaromaticity with a paratropic ring‐current, while 18π‐electron BzTAP 2 shows weakly aromatic character with NIR inertness. Notably, the NIR‐silent BzTAP 2 was readily converted to the NIR‐active BzTAP 1 in the presence of mild reducing agents such as amine. The intense NIR absorption band of BzTAP 1 is in sharp contrast to the very weak absorption bands of previously reported antiaromatic porphyrinoids. Molecular orbital analysis revealed that symmetry‐lowering perturbation of the 20π‐electron porphyrinoid skeleton enables the HOMO–LUMO transition of 1 to be electric‐dipole‐allowed. BzTAPs are expected to be useful for constructing activatable NIR probes working in reductive environments.

Activatable near‐infrared (NIR) dyes responsive to external stimuli are used in medical and other applications. Here, we describe the design and synthesis of bench‐stable 18π‐ and 20π‐electron benzitetraazaporphyrins (BzTAPs) possessing redox‐switchable NIR properties. X‐Ray, NMR, and UV/Visible‐NIR analyses revealed that 20π‐electron BzTAP 1 exhibits NIR absorption and antiaromaticity with a paratropic ring‐current, while 18π‐electron BzTAP 2 shows weakly aromatic character with NIR inertness. Notably, the NIR‐silent BzTAP 2 was readily converted to the NIR‐active BzTAP 1 in the presence of mild reducing agents such as amine. The intense NIR absorption band of BzTAP 1 is in sharp contrast to the very weak absorption bands of previously reported antiaromatic porphyrinoids. Molecular orbital analysis revealed that symmetry‐lowering perturbation of the 20π‐electron porphyrinoid skeleton enables the HOMO–LUMO transition of 1 to be electric‐dipole‐allowed. BzTAPs are expected to be useful for constructing activatable NIR probes working in reductive environments.