Rigidity‐Tuned Full‐Color Emission: Uncommon Luminescence Change from Polymer Free‐Volume Variations

Probing the rigidity change of microenvironments via tracking embedded molecular fluorophore emissions represents a robust approach to monitor various polymer microstructural evolutions and biomolecular events with a high spatiotemporal resolution. However, reported fluorophores exclusively blueshift their emissions (termed as "rigidochromism") or merely alter intensities upon rigidification, suffering from inferior sensitivities, low-contrast outputs, and attenuated biocompatibilities. Here, phenanthridine-fused triazatruxene fluorophores (PTFs) with pronounced bathochromic emission (up to 135 nm) toward rigidifying media at a low loading of 5 ppm without sacrificing the quantum yields and lifetime are developed. PTFs effectively interact with polymeric matrixes through polar-π interactions and form charge-transfer complexes, resulting to a remarkable fluorescent color change from blue to red-orange over matrix rigidifying. Such a unique anti-rigidochromism enables a highly sensitive rigidity detection (i.e., a subtle polymer molecular-weight change (as low as 1000 Da vs up to 10 kDa for conventional probes) can result to obvious emission color changes). PTFs are able to noninvasively detect polymerization kinetics and in situ optically report polymer degradations. The broadly (nearly full-spectrum) tunable emission and the efficient coupling between anti-rigidochromism and polymer hierarchical structures/topologies render fluorescence with controlled wavelength and chirality, leading to an unprecedented free-volume-based data encryption and anti-counterfeiting technology with a superhigh security level.