Amine-directed synthesis, valence state control, and optical properties of two new organic–inorganic tin chlorides

Abstract

Two organic–inorganic tin chlorides, namely (C₉H₂₆N₃Cl)SnCl₄ (1) and (C₉H₂₆N₃Cl)SnCl₆ (2), were prepared via valence state control using N,N,N′,N′′,N′′-pentamethyldiethylenetriamine as a structure-directing agent. The two compounds have zero-dimensional structures crystallized in non-centrosymmetric orthorhombic space group Cmc2₁ and P2₁2₁2₁, respectively. In compound 1, the divalent tin ion forms a seesaw coordination configuration with four chloride ions, whereas in compound 2, the tetravalent tin ion forms an octahedral coordination configuration with six chloride ions. The two compounds show a moderate second-harmonic generation response under 1064 nm laser irradiation. Notably, compound 2 displays a bright orange luminescence with a photoluminescence quantum yield of 19.67%. Theoretical calculations were performed to gain insights into the optical properties of the two compounds.