Crystal structure and optical properties characterization in quasi-0D lead-free organic-inorganic hybrid crystals (C6H16N)2MX4 (M = Zn, Mn; X = Br, Cl)

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry Pub Date : 2025-04-26 DOI:10.1016/j.jssc.2025.125396

Zhixu Liu , Jiayou Zhang , Yifan Xu , Pengcheng Li , Xiaochen Zhao , Wei Zhou , Shouyu Wang , Weifang Liu

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Abstract

Organic-inorganic hybrid perovskites are promising for optoelectronic applications due to their tunable band gaps and exceptional photophysical properties. We synthesized three perovskite derivatives, (C₆H₁₆N)₂ZnBr₄ (1), (C₆H₁₆N)₂MnBr₄ (2), and (C₆H₁₆N)₂MnCl₄ (3), via solution evaporation. Single-crystal X-ray diffraction confirmed monoclinic structures (space group P21/n) with refined reliability factors (1: R1 = 0.0915, wR2 = 0.2424; 2: R1 = 0.0238, wR2 = 0.0582). Lattice parameters for 1 (a = 9.4029(2) Å, b = 18.1735(4) Å, c = 12.9582(3) Å) and 2 (a = 9.3503(10) Å, b = 18.2398(10) Å, c = 12.8888(10) Å) indicate structural consistency. Experimental band gaps (4.45 eV for 1, 1.6 eV for 2, 2.96 eV for 3) align with first-principles calculations (4.51, 2.74, 2.87 eV). Thermogravimetric analysis revealed thermal stability below 250 °C. Notably, 1 exhibits unusual blue emission (quantum yield: 0.12 %, lifetime: 5.97 ns), while Mn-doped 2 and 3 show green luminescence with enhanced efficiencies (quantum yields: 14.6 % and 47.7 %; lifetimes: 1.08 μs and 32.52 μs). First-principles calculations further identify antiferromagnetic ordering in 2 and 3 due to Mn-3d interactions. The high quantum yield (47.7 %) and prolonged lifetime (32.52 μs) of 3 demonstrate its potential as a luminescent material.

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准d无铅有机-无机杂化晶体（C6H16N）2MX4 （M = Zn, Mn）的晶体结构和光学性质表征X = Br, Cl)

有机-无机杂化钙钛矿由于其可调的带隙和特殊的光物理性质而在光电应用中具有广阔的前景。通过溶液蒸发合成了三种钙钛矿衍生物（C6H16N）2ZnBr4(1)、（C6H16N）2MnBr4(2)和（C6H16N）2MnCl4(3)。单晶x射线衍射证实单斜晶结构（空间群P21/n）具有细化的可靠性因子(1:R1 = 0.0915, wR2 = 0.2424；2: R1 = 0.0238, wR2 = 0.0582)。1 (a = 9.4029(2) Å， b = 18.1735（4) Å， c = 12.9582(3) Å）和2（a = 9.3503（10） Å， b = 18.2398（10） Å， c = 12.8888（10） Å）的晶格参数表示结构一致性。实验带隙（1为4.45 eV， 2为1.6 eV， 3为2.96 eV）与第一性原理计算结果（4.51,2.74,2.87 eV）一致。热重分析显示其在250°C以下具有热稳定性。值得注意的是，1表现出不同寻常的蓝色发光（量子产率：0.12%，寿命：5.97 ns），而mn掺杂2和3表现出绿色发光，效率提高(量子产率：14.6%和47.7%；寿命分别为1.08 μs和32.52 μs)。第一性原理计算进一步确定了Mn-3d相互作用导致的2和3的反铁磁有序。3的高量子产率（47.7%）和长寿命（32.52 μs）证明了其作为发光材料的潜力。

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来源期刊

Journal of Solid State Chemistry 化学-无机化学与核化学

CiteScore

6.00

自引率

9.10%

发文量

848

审稿时长

25 days

期刊介绍： Covering major developments in the field of solid state chemistry and related areas such as ceramics and amorphous materials, the Journal of Solid State Chemistry features studies of chemical, structural, thermodynamic, electronic, magnetic, and optical properties and processes in solids.