Near‐Infrared Absorbing Para‐Azaquinodimethane Conjugated Polymers Synthesized via The Transition‐Metal‐Free Route Towards Efficient Photothermal Conversion

Abstract Conjugated polymers with strong absorption in the second near‐infrared (NIR‐II) window have multiple applications. However, the development of new type of NIR‐II conjugated polymers via facile and green methods remains challenging. Herein, this work reports a mild and convenient transition‐metal‐free method to synthesize near‐infrared absorbing quinoidal conjugated polymers containing para ‐azaquinodimethane (AQM) moieties. The AQM quinoidal conjugated polymers with unique molecular structures and tunable optoelectronic properties can be synthesized by combining the Knoevenagel polycondensation of aromatic dialdehyde monomers with commercially available 1,4‐diacetyl‐2,5‐piperazinedione and the following alkylation reaction. The resultant polymer PQ‐DPP shows remarkable NIR‐II absorption with a narrow band gap of about 1.08 eV. PQ‐DPP nanoparticles exhibit high photothermal conversion efficiency of up to 48% under 1064 nm laser irradiation (1 W cm −2 ) endowing this polymer with potential in bio‐related applications.