Mn‐doping in cesium lead halide perovskite nanoplatelets (NPls) is of particular importance where strong quantum confinement plays a significant role towards the exciton–dopant coupling. In this work, we report an immiscible bi‐phasic strategy for post‐synthetic Mn‐doping of CsPbX3 (X=Br, Cl) NPls. A systematic study shows that electron‐donating oleylamine acts as a shuttle ligand to transport MnX2 through the water–hexane interface and deliver it to the NPls. The halide anion also plays an essential role in maintaining an appropriate radius of Mn2+ and thus fulfilling the octahedral factor required for the formation of perovskite crystals. By varying the thickness of parent NPls, we can tune the dopant incorporation and, consequently, the exciton‐to‐dopant energy transfer process in doped NPls. Time‐resolved optical measurements offer a detailed insight into the exciton‐to‐dopant energy transfer process. This new approach for post‐synthetic cation doping paves a way towards exploring the cation exchange process in several other halide perovskites at the polar–nonpolar interface.

Photocatalytic water splitting is a promising approach to generating sustainable hydrogen. However, the transport of photoelectrons to the catalyst sites, usually within ps‐to‐ns timescales, is much faster than proton delivery (∼μs), which limits the activity. Therefore, the acceleration of abstraction of protons from water molecules towards the catalytic sites to keep up with the electron transfer rate can significantly promote hydrogen production. The photobasic effect that is the increase in proton affinity upon excitation offers means to achieve this objective. Herein, we design photobasic carbon dots and identify that internal pyridinic N sites are intrinsically photobasic. This is supported by steady‐state and ultrafast spectroscopic measurements that demonstrate proton abstraction within a few picoseconds of excitation. Furthermore, we show that in water, they form a unique four‐level lasing scheme with optical gain and stimulated emission. The latter competes with photocatalysis, revealing a rather unique mechanism for efficiency loss, such that the stimulated emission can act as a toggle for photocatalytic activity. This provides additional means of controlling the photocatalytic process and helps the rational design of photocatalytic materials.

Photocatalytic water splitting is a promising approach to generating sustainable hydrogen. However, the transport of photoelectrons to the catalyst sites, usually within ps-to-ns timescales, is much faster than proton delivery (μ s), which limits the activity. Therefore, the acceleration of abstraction of protons from water molecules towards the catalytic sites to keep up with the electron transfer rate can significantly promote hydrogen production. The photobasic effect that is the increase in proton affinity upon excitation offers means to achieve this objective. Herein, we design photobasic carbon dots and identify that internal pyridinic N sites are intrinsically photobasic. This is supported by steady-state and ultrafast spectroscopic measurements that demonstrate proton abstraction within a few picoseconds of excitation. Furthermore, we show that in water, they form a unique four-level lasing scheme with optical gain and stimulated emission. The latter competes with photocatalysis, revealing a rather unique mechanism for efficiency loss, such that the stimulated emission can act as a toggle for photocatalytic activity. This provides additional means of controlling the photocatalytic process and helps the rational design of photocatalytic materials.

Mn-doping in cesium lead halide perovskite nanoplatelets (NPls) is of particular importance where strong quantum confinement plays a significant role towards the exciton-dopant coupling. In this work, we report an immiscible bi-phasic strategy for post-synthetic Mn-doping of CsPbX 3 (X = Br, Cl) NPls. A systematic study shows that electron-donating oleylamine acts as a shuttle ligand to transport MnX 2 through the waterhexane interface and deliver it to the NPls. The halide anion also plays an essential role in maintaining an appropriate radius of Mn 2 + and thus fulfilling the octahedral factor required for the formation of perovskite crystals. By varying the thickness of parent NPls, we can tune the dopant incorporation and, consequently, the exciton-to-dopant energy transfer process in doped NPls. Time-resolved optical measurements offer a detailed insight into the exciton-to-dopant energy transfer process. This new approach for post-synthetic cation doping paves a way towards exploring the cation exchange process in several other halide perovskites at the polar-nonpolar interface.