Engineering Soluble Diketopyrrolopyrrole Chromophore Stacks from a Series of Pd(II)-Based Ravels.

A strategy to engineer the stacking of diketopyrrolopyrrole (DPP) dyes based on non-statistical metallosupramolecular self-assembly is introduced. For this, the DPP backbone is equipped with nitrogen-based donors that allow for different discrete assemblies to be formed upon the addition of Pd(II), distinguished by the number of π-stacked chromophores. A Pd ₃ L ₆ three-ring, a heteroleptic Pd ₂ L ₂ L' ₂ ravel composed of two crossing DPPs (flanked by two carbazoles), and two unprecedented self-penetrated motifs (a Pd ₂ L ₃ triple and a Pd ₂ L ₄ quadruple stack), were obtained and systematically investigated. With increasing counts of stacked chromophores, UV/Vis absorptions red-shift and emission intensities decrease, except for compound Pd ₂ L ₂ L' ₂ , which stands out with an exceptional photoluminescence quantum yield of 51 %. This is extraordinary for open-shell metal containing assemblies and explainable by an intra-assembly FRET process. The modular design and synthesis of soluble multi-chromophore building blocks offers the potential for the preparation of nanodevices and materials with applications in sensing, photo-redox catalysis and optics.
(© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)