Sustainable access to perylenedicarboxylic monoimides and diesters enables processable 3,3′-biperylene derivatives with large Stokes shifts

Dimeric 3,3 '-biperylenes derivatives derived from perylene-3,4-dicarboxylic monoimides (PMIs) and perylene-3,4-diesters (PDEs) represent promising yet underexplored alternatives to classical perylene-3,4,9,10-diimides (PDIs) and perylene-3,4,9,10-tetraesters (PTEs). In contrast to these widely used systems, 3,3 '-biperylenes derivatives combine high absorption coefficients with intrinsically large Stokes shifts arising from excited-state structural reorganization, while displaying minimal solvatochromism and reduced aggregation. These features are highly advantageous for wavelength-shifting applications, where reabsorption losses and environmental sensitivity limit the performance of conventional chromophores. Their limited adoption has been primarily dictated by the poor accessibility of 3,4-perylenedicarboxylic monoanhydride (PDCMA), the key synthetic intermediate. Here, we leverage a scalable and sustainable synthesis of PDCMA to establish a practical platform for the preparation of PMIs, PDEs, and their corresponding dimers. The resulting materials outperform PDIs and PTEs in terms of spectral separation, and can be readily incorporated into photopolymerizable resins to yield transparent, luminescent 3D objects while preserving their optical properties at high loadings.