Feng Shangwei, Huang Qiuqin, Yang Shuming, Lin Zhenghuan, Ling Qidan
Fujian Key Laboratory of Polymer Materials, College of Chemistry and Materials Science, Fujian Normal University Fuzhou 350007 China
Chem Sci. 2021 Oct 11;12(43):14451-14458. doi: 10.1039/d1sc04806f. eCollection 2021 Nov 10.
Organic-inorganic hybrid metal halides have attracted intensive attention because of their unique electronic structure and solution processability. They have a rigid micro/nano-structure and heavy atom effect, which has obvious advantages in promoting organic room temperature phosphorescence (RTP). However, the toxicity of heavy metals has limited their further development. Herein, two metal-free 2D layered ammonium halides, homopiperonylammonium bromide and chloride (HLB and HLC), are described for the first time. Their layered structure consists of rigid inorganic ammonium halide laminates and neatly stacked organic layers. The rigid laminates and external heavy atom effect of halogen atoms make HLB and HLC produce green RTP. When phosphor guests with different triplet energies are doped into HLB, HLC, or phenylethylamine salt hosts, effective full-color and even white ultra-long RTP with phosphorescence quantum yield up to 18.7% and lifetime up to 1.7 s is realized through energy transfer between the host and guest. Due to the simple solution synthesis, 10 g-level doped layered organic ammonium halides with the same phosphorescence properties can be easily obtained. The information ink based on these doped halides and non-toxic ethanol solvent can form various patterns on filter paper. The fluorescence and phosphorescence of these patterns are sensitive to the excitation wavelength and acid-base vapor. Consequently, they can be applied to multiple complex anti-counterfeiting and fluorescence/phosphorescence dual-mode chemical sensors.
有机-无机杂化金属卤化物因其独特的电子结构和溶液可加工性而备受关注。它们具有刚性的微/纳米结构和重原子效应，在促进有机室温磷光（RTP）方面具有明显优势。然而，重金属的毒性限制了它们的进一步发展。在此，首次描述了两种无金属的二维层状卤化铵，高哌啶鎓溴化物和氯化物（HLB和HLC）。它们的层状结构由刚性无机卤化铵层板和整齐堆叠的有机层组成。刚性层板和卤素原子的外部重原子效应使HLB和HLC产生绿色RTP。当将具有不同三重态能量的磷光客体掺杂到HLB、HLC或苯乙胺盐主体中时，通过主体与客体之间 的能量转移，实现了有效的全色甚至白色超长RTP，磷光量子产率高达18.7%，寿命长达1.7秒。由于合成方法简单，通过溶液法可以轻松获得10克级具有相同磷光性质的掺杂层状有机卤化铵。基于这些掺杂卤化物和无毒乙醇溶剂的信息墨水可以在滤纸上形成各种图案。这些图案的荧光和磷光对激发波长和酸碱蒸汽敏感。因此，它们可应用于多种复杂的防伪和荧光/磷光双模式化学传感器。
