Novel 3D Cubic Topology in Hybrid Lead Halides with a Symmetric Aromatic Triammonium Exhibiting Water Stability

Abstract

The limitations of three-dimensional (3D) perovskites are related to their narrow structural tunability of the organic cations and their moisture sensitivity. Herein, we report a new family of 3D cubic hybrid metal halides (T-Et 6 ) 3 Pb 11 X 31 (X = I, Br), where T is 1,3,5-tris-(4aminophenyl)benzene. The materials are synthesized through an in situ Nalkylation of T and an efficient one-step solvothermal reaction containing ethanol, initiating a tunable synthetic avenue for the acquisition of structurally complex hybrid halides with luminophores. (T-Et 6 ) 3 Pb 11 X 31 consist of an unprecedented Ia3̅ framework of [Pb 11 X 31 ] 9− onedimensional (1D) chains embedded with (T-Et 6 ) 3+ cations, affording an overall 3D topology. The constituent [Pb 11 X 31 ] 9− chains include exclusively octahedral lead halide units with clusters of face-and edgesharing connectivity, giving rise to weak broad emission centered at ∼660 nm observed at 78 K. (T-Et 6 ) 3 Pb 11 I 31 demonstrates water stability for at least 7 days. Synthesis through ambient pressure results in tunable structural variations of zero-dimensional (0D) structures rendering T 7 Pb 3 Br 27 •DMF and T 2 Sn 3 Br 18 •4H 2 O•0.5Br 2 , both of which feature blue PL emission at room temperature.