The Dynamic Organic/Inorganic Interface of Colloidal PbS Quantum Dots

Colloidal quantum dots are composed of nanometer‐sized crystallites of inorganic semiconductor materials bearing organic molecules at their surface. The organic/inorganic interface markedly affects forms and functions of the quantum dots, therefore its description and control are important for effective application. Herein we demonstrate that archetypal colloidal PbS quantum dots adapt their interface to the surroundings, thus existing in solution phase as equilibrium mixtures with their (metal‐)organic ligand and inorganic core components. The interfacial equilibria are dictated by solvent polarity and concentration, show striking size dependence (leading to more stable ligand/core adducts for larger quantum dots), and selectively involve nanocrystal facets. This notion of ligand/core dynamic equilibrium may open novel synthetic paths and refined nanocrystal surface‐chemistry strategies. Colloidal quantum dots adapt their composition to their surroundings, existing in the solution phase as equilibrium mixtures with their (metal‐)organic ligand and inorganic core components. The inherently dynamic organic/inorganic interface of colloidal quantum dots may open novel possibilities towards improved synthetic procedures and effective surface‐chemistry strategies.