Charge Transfer Dynamics\nin Supramolecular Tessellations\nComposed of Aromatic Donors and Chiral Tris(naphthalenediimide) Triangular\nAcceptors

Understanding charge transfer (CT) dynamics in donor–acceptor\n(D–A) cocrystals is important for the development of efficient\norganic photovoltaic and electronic materials. This study explores\nthe photogenerated CT states of supramolecular tessellations formed\nby cocrystallizing a chiral tris(naphthalenediimide) triangular prism\n(−)-NDI-Δ with pyrene, perylene, and <i>peri</i>-xanthenoxanthene electron donors. By manipulating crystallization\nconditions, one-dimensional (1D) and two-dimensional (2D) cocrystals\nwith distinct structural motifs and morphologies are achieved. Femtosecond\nand nanosecond transient absorption microscopies and time-resolved\nelectron paramagnetic resonance spectroscopy were employed to elucidate\nthe CT state dynamics. Our findings reveal that the CT state lifetimes\nare lengthened in the 2D cocrystals relative to the 1D cocrystals,\nwhich is attributable to the symmetry and molecular packing differences\nbetween them that modulate the CT interactions. This work highlights\nthe potential of using preorganized covalent multisite charge carriers\nas donors or acceptors in cocrystals as a strategy for engineering\nstructures for advanced multifunctional materials with tunable CT\nproperties.