Intermolecular arrangement facilitated broadband blue emission in group-12 metal (Zn, Cd) hybrid halides and their applications
Intermolecular arrangement facilitated broadband blue emission in group-12 metal (Zn, Cd) hybrid halides and their applications
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DOI：
10.1016/j.mtchem.2023.101502
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发表时间：
2023-06
影响因子：
7.3
通讯作者：
D. Popy;B. Evans;J. Jiang;T. Creason;D. Banerjee;L. M. Loftus;R. Pachter;D. Glatzhofer;B. Sa
中科院分区：
文献类型：
--
作者：
D. Popy;B. Evans;J. Jiang;T. Creason;D. Banerjee;L. M. Loftus;R. Pachter;D. Glatzhofer;B. Sa
各种荧光有机材料因其在发光二极管、有机激光器、防伪和生物成像等方面的潜在应用而广为人知。然而，差的发射效率和稳定性问题限制了它们的可用性。本文报道了两个新的有机-无机杂化12族卤化物（P-xd）ZnCl_4和（P-xd）CdCl_4（其中（P-xd）=对苯二甲撑二铵）的合成、晶体结构、电子结构和光学性质。这两种化合物的单晶可以通过溶液化学方法从它们的低成本、低毒性和容易获得的前体方便地合成。（P-xd）ZnCl 4具有晶体结构，其特征在于有机阳离子和完全分离的零维（0 D）连接的阴离子[ZnCl 4]2-四面体单元的交替层。相比之下，（P-xd）CdCl 4采用类似的有机阳离子层，夹在二维（2D）连接的钙钛矿片之间，这些钙钛矿片是由角共享阴离子[CdCl 6]4-八面体单元形成的。结构，光学和电子学的研究表明，将有机和无机结构单元掺入到混合结构中提高了其蓝光发射效率，在（P-xd）ZnCl 4和（P-xd）CdCl 4中的光致发光量子产率（PLQY）值分别比有机前体高近23倍和4倍。值得注意的是，（P-xd）ZnCl 4的PLQY为23%，是迄今为止报道的Zn基混合有机-无机金属卤化物的最高PLQY，其中发射源自有机组分。（P-xd）ZnCl 4和（P-xd）CdCl 4都表现出显著改善的空气稳定性、热稳定性和光稳定性，这表明它们适合于潜在的实际应用，如指纹检测和固态照明。
Various fluorescent organic materials are widely known for their potential applications in light-emitting diodes, organic lasers, anti-counterfeiting and bio-imaging. However, poor emission efficiency and stability issues limit their usability. Here we report the syntheses, crystal and electronic structures, and optical characterizations of two new hybrid organic-inorganic group 12 halides, (P-xd)ZnCl4and (P-xd)CdCl4(where (P-xd) =p-xylylenediammonium). Single crystals of both compounds can be conveniently synthesized by solution chemistry methods from their low-cost, low toxicity and easily available precursors. (P-xd)ZnCl4possesses a crystal structure featuring alternating layers of organic cations and completely separated anionic [ZnCl4]2-tetrahedral units of zero-dimensional (0D) connectivity. In contrast, (P-xd)CdCl4adopts similar layering of organic cations sandwiched between perovskite sheets of two-dimensional (2D) connectivity, which are formed by corner-sharing anionic [CdCl6]4-octahedral units. The structural, optical, and electronic studies suggest that the incorporation of organic and inorganic structural units into a hybrid structure improves its blue emission efficiency with nearly 23 times and 4 times higher photoluminescence quantum yield (PLQY) values in (P-xd)ZnCl4and (P-xd)CdCl4, respectively, as compared to the organic precursor. Notably, PLQY of 23% for (P-xd)ZnCl4is the highest reported to date for Zn-based hybrid organic-inorganic metal halides, where emission originates from the organic component. Both (P-xd)ZnCl4and (P-xd)CdCl4demonstrate considerably improved air-, thermal- and photostability, which suggest their suitability for potential practical applications such as fingerprint detection and solid-state lighting.