Polycyclic　aromatic　hydrocarbons　(PAHs)　have　attracted　significant　interest　in　material　chemistry,　particularly　if　they　own　extremely　low　band　gaps　and　magnetic　properties.　However,　challenges　remain　regarding　the　synthetic　accessibility　and　energy　saturation　issues.　In　this　study,　we　introduce　NR-11,　which　consists　of　eleven　aromatic　rings　in　its　main　conjugation　and　is　separately　doped　with　two　electron-rich　nitrogen　atoms.　This　unique　structure　imparts　intriguing　oxidation　characteristics　to　NR-11.　The　cationic　radical　NR-11+center　dot　exhibits　enhanced　stability　and　demonstrates　strong　absorption　in　the　range　of　1250　nm　to　3000　nm,　peaking　at　2570　nm.　As　a　result,　the　optical　energy　gap　of　NR-11+center　dot　is　one　of　the　lowest　reported　to　date.　Additionally,　X-ray　crystal　structure　analysis　reveals　that　NR-11+center　dot　displays　unusual　symmetry-broken　charge　separation.　For　the　dication,　variable-temperature　NMR　and　variable-temperature　EPR　studies　indicate　that　NR-112+　exhibits　a　high　diradical　character　with　a　Delta　ES-T　of　approximately　-1　kcal/mol.　Additionally,　its　spins　are　polarized　at　two　ends　of　the　PAH.　Meanwhile,　its　strong　absorption　in　the　near-infrared　II　region　suggests　promise　in　photoacoustic　(PA)　conversion　applications.　This　work　underscores　the　significance　of　cationic　species　of　extended　long　PAHs,　highlighting　their　exceptional　properties　and　potential　applications.