Characterized by their strong 1D confinement and long‐lifetime red‐shifted emission spectra, colloidal nanoplatelets (NPLs) with type‐II electronic structure provide an exciting ground to design complex heterostructures with remarkable properties. This work demonstrates the synthesis and optical characterization of CdSe/CdSeTe/CdTe core/crown/crown NPLs having a step‐wise gradient electronic structure and disproportional wavefunction distribution, in which the excitonic properties of the electron and hole can be finely tuned through adjusting the geometry of the intermediate crown. The first crown with staggered configuration gives rise to a series of direct and indirect transition channels that activation/deactivation of each channel is possible through wavefunction engineering. Moreover, these NPLs allow for switching between active channels with temperature, where lattice contraction directly affects the electron–hole (e–h) overlap. Dominated by the indirect transition channels over direct transitions, the lifetime of the NPLs starts to increase at 9 K, indicative of low dark‐bright exciton splitting energy. The charge transfer states from the two type‐II interfaces promote a large number of indirect transitions, which effectively increase the absorption of low‐energy photons critical for nonlinear properties. As a result, these NPLs demonstrate exceptionally high two‐photon absorption cross‐sections with the highest value of 12.9 × 106 GM and superlinear behavior.

Multi‐Crown Type‐II Nanoplatelets In article number 2205729, Hilmi Volkan Demir and co‐workers discuss the recombination dynamics of CdSe/CdSeTe/CdTe core/crown/crown nanoplatelets (NPLs) with a step‐wise gradient electronic structure. The NPLs possess disproportional electron and hole wavefunction distributions, in which the activation/deactivation of direct and indirect channels is possible by adjusting the domains' geometry. These NPLs demonstrate exceptionally high two‐photon absorption cross‐section and low dark‐bright exciton splitting energy.