Funder: Studienstiftung des Deutschen Volkes; doi: http://dx.doi.org/10.13039/501100004350Funder: Winton Programme for the Physics of SustainabilityFunder: Rowland Institute at Harvard; doi: http://dx.doi.org/10.13039/100009835A strategy to engineer the stacking of diketopyrropyrrole (DPP) dyes based on non‐statistical metallosupramolecular self‐assembly is introduced. Therefore, the DPP backbone is equipped with nitrogen‐based donors that allow for different discrete assemblies to be formed upon addition of Pd(II), distinguished by the number of π‐stacked chromophores. A Pd3L6 three‐ring, a heteroleptic Pd2L2L’2 ravel composed of two crossing DPPs (flanked by two carbazoles), and two unprecedented self‐penetrated motifs (a Pd2L3 triple and a Pd2L4 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 Pd2L2L’2 which stands out with an exceptional photoluminescence quantum yield of 52%. 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 opens potential for the preparation of nanodevices and materials with applications in sensing, photo‐redox catalysis and optics.</jats:p
