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Authors
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Bouajhine, M. e. h.; Kielesiński, L.; Levichkova, M.; Bittrich, E.; Bartosch, S.; Scheler, U.; Uhlmann, P.; Brocorens, P.; Lemaur, V.; Giannini, S.; Pfeiffer, M.; Walzer, K.; Gryko, D. T.; Beljonne, D.
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Title
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Dipyrrolonaphthyridinedione aggregation in the solid state - the importance of side-chain geometry
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Date
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27.03.2026
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Number
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0
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Abstract
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The aggregation behavior of dipyrrolonaphthyridinedione (DPND) chromophores in the solid state critically determines their optoelectronic properties. Here, we investigate how systematic variation in the side-chain geometry─specifically the branching point and steric profile─governs molecular packing and excitonic coupling. Using crystal structure prediction (CSP) combined with experimental GIWAXS and solid-state NMR, we obtain the packing geometry and crystal structure for three DPND derivatives (DPND-iPr, DPND-EtPr, and DPND-iBu). The results reveal that side-chain branching at the first carbon atom promotes herringbone packing and J-type behavior, while branching at the second carbon induces brick-wall stacking and H-type behavior in the solid state. Optical simulations based on the Holstein exciton-vibrational Hamiltonian reproduce experimental absorption and photoluminescence spectra, confirming the transition from J-like to H-like photophysics as the side-chain branching position shifts. This study demonstrates that fine-tuning alkyl side-chain geometry enables rational control of aggregation and excitonic behavior in cross-conjugated DPNDs, providing new design principles for functional organic semiconductors.
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Publisher
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American Chemical Society
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Wikidata
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Citation
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Journal of Physical Chemistry C 130 (2026) 5171-5181
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DOI
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https://doi.org/10.1021/acs.jpcc.6c00180
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