Organolead Halide-Based Coordination Polymers: Intrinsic Stability and Photophysical Applications

Abstract

Metrics & MoreArticle Recommendations CONSPECTUS: Organolead halide-based photovoltaics are one of the state-of-theart solar cell systems with efficiencies increasing to 25% over the past decade, ascribed to their high light-absorption coefficient, broad wavelength coverage, tunable band structure, and excellent carrier mobility. Indeed, these optical characteristics are highly demanding in photocatalysis and photoluminescence (PL), which also involve the solar energy utilization and charge transport. However, the vast majority of organolead halides are ionically bonded structures and susceptible to degradation upon high-polarity protic molecules (e.g., water (vapor) and alcohol), which are often inevitable in many photochemical applications.Encapsulation is a commonly used stabilization approach by coating protective layers, avoiding the direct contact between organolead halides and polar molecules. However, this may partially hinder the light penetration to the inner hybrid halide

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

“…In the free Mn 2+ ion, the ground energy term 6s becomes 6 A 1 energy level with electronic configuration of t 3 2 e 2 , and the excited energy states of 4 G, 4 D, and 4 P split into six low-lying energy subterms in the presence of crystal field. Specifically, 4 G, 4 D, and 4 P terms split into six closely spaced…”

“…Specifically, the weak crystal field is associated with higher-energy green light emission, and strong crystal field gives rise to lower-energy red light emission. [53][54][55][56] Based on the T-S energy level diagram, the absorption bands at 224 (44 642 cm −1 ), 312 (32 051 cm −1 ), 360 (27 777 cm −1 ), 433 (23 059 cm −1 ), and 448 nm (22 321 cm −1 ) can be defined as electron transitions of 6 A 1 ( 6 S)→ 4 T 1 ( 4 P), 6 A 1 ( 6 S)→ 4 E( 4 D), 6 A 1 ( 6 S)→ 4 T 2 ( 4 D), 6 A 1 ( 6 S)→ 4 E( 4 G), 4 A 1 ( 4 G), and 6 A 1 ( 6 S)→ 4 T 2 ( 4 G), respectively, in the [MnCl 4 ] 2− tetrahedron of [H 2 TMDAP]Mn 0.63 Zn 0.37 Cl 4 (Figure 4b). Similarly, all the absorption peaks of [H 2 TMDAP] 3 [MnCl 4 ] 2 [Mn 2 Cl 6 ] can be successively assigned as the d-d transition from excited states to ground level as illustrated in Figure 4c.…”

“…The obtained D q /B values of [H 2 TMDAP]Mn 0.63 Zn 0.37 Cl 4 and [H 2 TMDAP] 3 [MnCl 4 ] 2 [Mn 2 Cl 6 ] are 0.87 and 1.13, respectively. The relatively smaller ratio of D q /B in is [H 2 TMDAP]Mn 0.63 Zn 0.37 Cl 4 corresponding to weak crystal field, which results in large energy separation between 6 A 1 ( 6 S) and 4 T 1 ( 4 G) as well as higher-energy green light emission (521 nm). Comparing with [H 2 TMDAP]Mn 0.63 Zn 0.37 Cl 4 , the higher D q /B ratio in [H 2 TMDAP] 3 [MnCl 4 ] 2 [Mn 2 Cl 6 ] demonstrates that the absorption bands are derived from the stronger crystal field of octahedral [MnCl 6 ] unit, which leads to small energy difference between 6 A 1 ( 6 S) and 4 T 1 ( 4 G), and hence red light emission occurs at lower-energy (630 nm).…”

“…Br, I) have attracted tremendous attention owing to the excellent photoluminescent (PL) properties including high PLQY, narrow emission linewidth, tunable band gap and emission wavelength, and facile assembly process. [1][2][3][4][5][6][7] As a consequence, 3D PNCs are considered as nextgeneration photoelectric functional materials with application prospects in solidstate lighting, luminescent solar concentrators, anti-counterfeiting, scintillation, and laser. [8][9][10][11][12][13][14][15][16][17] Despite the tremendous achievement in luminescent field, the serious emission instability and toxicity of Pb 2+ extremely impede the wide applications.…”

Stable self-trapped broadband emission from an organolead halide coordination polymer with strong layer corrugation and high chemical robustness

“…Our group focused on using organocarboxylates as the interlamellar pillars to construct a family of layered organolead halide coordination polymers, which exhibit high robustness over a wide range of pH values and under aqueous boiling conditions. 18,19,23–26 This is largely ascribed to the Pb 2+ -carboxylate coordination motifs in our layered architectures that afford enhanced structural integrity, superior to the ionic bonded structures for perovskites. 19 In order to advance the elastic deformation and the role of STEs, great efforts have been made to decrease the inorganic dimensionality of lead halide sublattices in the coordination networks.…”