Water‐Stable 0D Hybrid Manganese Halides with Adjustable Crystal Structure and Emission Color

Abstract Despite the ultra‐high photoluminescence quantum yield (PLQY) of 0D hybrid manganese halides as state‐of‐the‐art luminescent materials, intrinsic water stability remains an unsurpassable barrier due to the serious hygroscopicity of the hydrogen‐bonding structure. Herein, a synthetic strategy that realizes adjustable emission color and high water resistance in a 0D hybrid manganese chloride family based on the same cation of [H 2 TMDAP] 2+ (TMDAP = N , N , N ′, N ′‐tetramethyl‐1,3‐diaminopropane) is reported. Specifically, direct solution or solid‐state reaction of precursor materials generates [H 2 TMDAP] 3 [MnCl 4 ] 2 [Mn 2 Cl 6 ], while additional Zn 2+ ‐doping as a structural directing agent results in [H 2 TMDAP]Mn 0.63 Zn 0.37 Cl 4 . Functionally, the [Mn/ZnCl 4 ] 2− tetrahedron based [H 2 TMDAP]Mn 0.63 Zn 0.37 Cl 4 displays green light emission at 521 nm with a PLQY of 63.9%. [H 2 TMDAP] 3 [MnCl 4 ] 2 [Mn 2 Cl 6 ] is composed of a [MnCl 6 ] 4− octahedron based [Mn 2 Cl 6 ] 2− chain and a discrete [MnCl 4 ] 2− tetrahedron, but it only exhibits single red emission at 628 nm with a PLQY of 48.1%. Compared with water‐instable [H 2 TMDAP]Mn 0.63 Zn 0.37 Cl 4 , [H 2 TMDAP] 3 [MnCl 4 ] 2 [Mn 2 Cl 6 ] represents extraordinary chemical stability in humid air and water over 1 month, manifested by an unchanged structural lattice and sufficient emission intensity. Significantly, the ultra‐high water proof performance of [H 2 TMDAP] 3 [MnCl 4 ] 2 [Mn 2 Cl 6 ] is nearly unmatchable among all previously reported manganese halides as far as is known. The combined merits of tunable emission wavelength, high PLQY, and stability highlight the potential applications of title materials in solid‐state lighting and display diodes.