Toward Multifunctional Polymer Hybrid through Tunable Charge Transfer Interaction of Anthracene/Naphthalenediimide

The interaction between building blocks in the polymer hybrids plays an important role in their performance and functions. Herein, a novel multifunctional polymer hybrid with tunable charge transfer (CT) interaction between π‐electron‐poor naphthalenediimide (NDI) containing polyimide (PI) and π‐electron‐rich anthracene (AN) ended polyhedral oligomer silsesquioxane (POSS‐AN) is reported (name the polymer hybrid “PI@POSS‐AN”), in which the presence of CT interaction between NDI and AN and its controllable feature are confirmed by UV−vis and fluorescence spectra. A new absorption band at 500 nm in the visible region appears and the emission maxima of the CT complexes are distinctly red‐shifted to 645 nm, while the fluorescence of NDI (493 nm) and AN (481 nm) are significantly quenched in the polymer hybrids. The resulting hybrid films are transparent and homogeneous, exhibit the enhanced thermal and mechanical performance with the increasing content of POSS‐AN. Thanks to the reversible photodimerization of AN, CT interaction between NDI and AN can be on‐off controlled in situ by UV light and heating, and rewritable fluorescence micro‐patterns with red and green emission can be obtained. In addition, the cross‐linked polymer hybrids possess healability and reprocessing performance.