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 [H2TMDAP]2+ (TMDAP = N,N,N′,N′‐tetramethyl‐1,3‐diaminopropane) is reported. Specifically, direct solution or solid‐state reaction of precursor materials generates [H2TMDAP]3[MnCl4]2[Mn2Cl6], while additional Zn2+‐doping as a structural directing agent results in [H2TMDAP]Mn0.63Zn0.37Cl4. Functionally, the [Mn/ZnCl4]2− tetrahedron based [H2TMDAP]Mn0.63Zn0.37Cl4 displays green light emission at 521 nm with a PLQY of 63.9%. [H2TMDAP]3[MnCl4]2[Mn2Cl6] is composed of a [MnCl6]4− octahedron based [Mn2Cl6]2− chain and a discrete [MnCl4]2− tetrahedron, but it only exhibits single red emission at 628 nm with a PLQY of 48.1%. Compared with water‐instable [H2TMDAP]Mn0.63Zn0.37Cl4, [H2TMDAP]3[MnCl4]2[Mn2Cl6] 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 [H2TMDAP]3[MnCl4]2[Mn2Cl6] 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.

Passivation of Organic–Inorganic Hybrid Perovskite with Poly(lactic Acid) to Achieve Stable Red-Light Flexible Films

“…29 Generally, the red-light lifetime of Mn 2+ ions is less than 7 ms with the characteristic excitation peak located in the visible region. 30,31 The photoluminescent spectra of PC-M excited at different wavelengths show the same emission peaks (Figure S7), confirming that the red emission of the crystals comes from only one emission center. Although the three organic cations have little effect on the luminescent color of PC-M, they result in significant difference in the luminescent efficiency of perovskites.…”

Photochromic Ln-Phosphonates Assembled by an Imidazole Derivative: Construction, Crystal Structures, and Light-Enhanced Proton Conductivity

“…Coordination polymers (CPs) assembled with metal ions/clusters and organic ligands are a class of crystalline complexes and have attracted great attention in sensing detection, separation, and adsorption due to their designable and tunable structures and functional porosity. − Recently, CPs have become a new candidate material for proton conduction as the hydrogen-bond networks could be formed through introducing typical ligands with hydrophilic units or proton carriers. − In this way, high-conductivity CPs are constructed with good proton transport paths. Most importantly, the visualization of the structure of CPs provides an opportunity to explore the proton conduction mechanism and pathway, which makes it possible to analyze the structure–property relationship in depth.…”