Hydrated Zirconium Coordination Enhanced the Photoluminescence Performance in 0D Cadmium Manganese Based Perovskites

Abstract

Mn2+ activated hybrid perovskites containing Cd are appealing single matrix emitters for tunable color and dual mode luminescence, yet in most Cd/Mn systems, absorption and sensitization are still regulated mainly by the inorganic [BCl6]4- sublattice, while the A site is treated as a passive countercation. Here we demonstrate that a coordination complex at the A site can instead become an active photophysical component by synthesizing 0D crystals of [ZrO(H2O)8]2BCl6 (B = Cd, Mn, Cd0.7Mn0.3), where isolated [BCl6]4- units are separated by a hydrated Zr-oxoaqua cation. All crystals share a dominant deep UV absorption band below ~300 nm and a broadband blue host emission (420–500 nm, τ ≈ 1.27–1.60 ns), while crystals containing Mn show ~620 nm Mn2+ emission with lifetimes on the millisecond timescale (2.70 ms for Mn and 3.33 ms for CdMn). This study shows that the Zr-oxoaqua framework at the A site can contribute to the host excitation manifold in the deep UV region and enable Mn2+ emission through host sensitization, while composition tuning modulates the balance between competing relaxation pathways