The First Organic-Inorganic Hybrid Luminescent Multiferroic: (Pyrrolidinium)MnBr3
The First Organic-Inorganic Hybrid Luminescent Multiferroic: (Pyrrolidinium)MnBr3
复制标题
第一个有机-无机杂化发光多铁性：(吡咯烷鎓)MnBr3
DOI：
10.1002/adma.201501026
复制
发表时间：
2015
影响因子：
29.4
通讯作者：
Xiong Ren-Gen
中科院分区：
文献类型：
--
作者：
Zhang Yi;Liao Wei-Qiang;Fu Da-Wei;Ye Heng-Yun;Liu Cai-Ming;Chen Zhong-Ning;Xiong Ren-Gen
DOI：10.1002/ADMA。201501026良好的铁电性能。[43，45，46]这样的AMX3结构涉及一大类化合物(A=一价有机氨阳离子；M=Mn，Fe，Co，Ni，Cu，Cr或V；X=Cl或Br.[47]其中，含锰化合物已被报道能发出明亮的红光。[48]因此，我们试图设计AMNX3型化合物，并发现了一种新的铁电化合物：(吡咯烷)MnBr3(1)(方案1)，它在紫外光激发下表现出强烈的红色发光。在这里，我们报告了它的制备，相变，铁电和发光性质，以及弱铁磁性(见辅助信息)。首先通过热分析和介电测量发现化合物1在T_c=219K附近经历了结构相变(图1a，c)。为了准确分析主要结构差异以了解铁电性的起源，我们测定了1at293和200K的晶体结构[49]为了便于比较结构变化，选择了共同的起源和相似的轴向。高温相(HTP)为斜方晶系，空间群为CMCM；低温相(LTP)呈极性空间群Cmc2 1。晶体结构为六方钙钛矿型结构，式为ABX 3与BaNiO 3的结构相同。晶体结构包含面状共用的CdBr6八面体(图2)的无限柱状结构，其排列方式与六方相2-H BaNiO 3中的NiO 6单元相同。两相中链的构型几乎相同，中心Mn原子的配位几何与其他ABX 3化合物，如(CH3)4NMnBr3[51](BrMnBr3[51]，2.695(4)-2.724(6)；相反的BR-原子角BR-Cd-BR为178.8(2)-180；相邻的BR-Cd-BR角BR-Cd-BR分别为84.25(13)和93.57(7)-96.53(18)，表明八面体有微弱的扭曲。八面体柱子之间的空穴被吡咯烷阳离子占据，类似于BaNiO3中的BaNiO3。在HTP中，吡咯烷阳离子位于2 mm对称性的特殊位置。吡咯烷阳离子采用非平面几何构型。有机-无机杂化化合物满足了晶体对称性的要求，近十年来，由于有机-无机杂化化合物结合了合成简便、有趣和可调的光电性能，因此受到越来越多光电材料研究者的关注。这些优点使它们适合于各种低成本的光电器件，如有机发光二极管、[2-15]和太阳能电池。
DOI: 10.1002/adma. 201501026 excellent ferrolectricity.[43, 45, 46] Such AMX 3 structures involve a large class of compounds (A= monovalent organic ammonium cation; M= Mn, Fe, Co, Ni, Cu, Cr, or V; X= Cl or Br).[47] Among them, Mn-containing compounds have been reported to emit brightly.[48] Thus, we tried to design AMnX 3-type compounds, and found a new ferroelectric:(pyrrolidinium) MnBr 3 (1)(Scheme 1), which exhibits intense red luminescence under a UV excitation. Here, we report its preparation, phase transition, ferroelectric and luminescent properties, as well as weak ferromagnetism (see Supporting Information). Compound 1 was found to undergo a structural phase transition at around Tc= 219 K first by thermal analysis and dielectric measurements (Figure 1 a, c). For precise analysis of the main structural differences to understand the origin of the ferroelectricity, we determined the crystal structures of 1at 293 and 200 K.[49] A common origin and similar axial directions were chosen to facilitate the comparison of the structural changes. The hightemperature phase (HTP) is orthorhombic, space group Cmcm; the low-temperature phase (LTP) assumes a polar space group Cmc2 1. The crystal structure is of the hexagonal perovskite-type structure with formula ABX 3 as that of BaNiO 3.[50] The crystal structures contain infinite columns of face-sharing CdBr 6 octahedra (Figure 2), arranged in the same manner as the NiO 6 unities in the hexagonal 2-H BaNiO 3. The configuration of the chains in both phases is almost the same, and the coordination geometries of the center Mn atom are comparable to those in other ABX 3 compounds, such as (CH 3) 4NMnBr 3[51](Br–Mn bond distances, 2.695 (4)–2.724 (6) Å; opposite Br-atom angles Br–Cd–Br are 178.8 (2)–180; adjacent Br-atoms angles Br–Cd–Br are 84.25 (13) and 93.57 (7)–96.53 (18), respectively, showing a weak distortion of the octahedron). The cavities between the octahedral columns are occupied by the pyrrolidinium cations, similar to the barium cations in BaNiO 3. In HTP, the pyrrolidinium cation is located on the special position with 2 mm symmetry. The pyrrolidinium cation adopts a nonplanar geometry. The crystal symmetry requirement is satisfied by theOrganic–inorganic hybrid compounds have attracted more and more attention of researchers in the field of optoelectronic materials over the last decade, because they combine facile synthesis with interesting and tunable optoelectronic properties.[1] These advantages make them suitable for a variety of low-cost optoelectronic devices, such as organic light-emitting diodes,[2–15] and solar cells.[16–18]