Li Ming, Ma Junying, Wang Junling, Wei Xuefeng, Lu Weiwei
School of Chemistry & Chemical Engineering, Henan University of Science and Technology, Luoyang, Henan 471023, People's Republic of China.
ACS Appl Mater Interfaces. 2025 Jan 15;17(2):4033-4043. doi: 10.1021/acsami.4c19789. Epub 2025 Jan 6.
The sensitive and selective identification of nitroaromatic explosives and industrially ubiquitous nitrates, which are harmful to the environment, is crucial from the viewpoints of security and environmental remediation. New multifunctional fluorescent porous materials that can sense nitro-explosives and nitrates are under continuous development. To this end, this study synthesizes 3,10,15-/-3,10,16-tribromotrinaphtho[3.3.3]propellane (TBP) and 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole (BB) and employs them as dual building blocks to prepare a porous conjugated microporous polymer (denoted as CMP-TBP-BB) via Suzuki-Miyaura borylation polycondensation. The CMP-TBP-BB synthesis strategy takes advantage of the donor and acceptor characteristics of the propeller-like trinaphtho[3.3.3]propellane moiety in TBP and the benzothiadiazole group in BB, respectively. The unusual two-dimensional conformation of the CMP with propeller-array-structured monomers helps to position the π components in the crystalline layers and establishes aligned conduction pathways. CMP-TBP-BB exhibits outstanding fluorescence characteristics. Its distinctive two-dimensional skeleton is exploited to fabricate highly aligned donor-acceptor building blocks, which is typically considered a challenging task. The porous CMP acts as a fluorescent sensor for selectively and sensitively detecting electron-deficient nitro-explosives and metal nitrates. Specifically, CMP-TBP-BB is responsive to 2,4,6-trinitrophenol and Fe(NO) at parts per million levels, and the results of combined experimental and theoretical investigations of its sensing properties highlight its potential as a CMP-based fluorescence probe. Additionally, the dual-function fluorescent CMP probe exhibits remarkable temperature-sensing behavior owing to the high linearity between the fluorescence intensity and temperature, making it an excellent fluorescent thermometer.
从安全和环境修复的角度来看，对硝基芳香族炸药以及工业上普遍存在的、对环境有害的硝酸盐进行灵敏且选择性的识别至关重要。能够检测硝基炸药和硝酸盐的新型多功能荧光多孔材料正在不断研发中。为此，本研究合成了3,10,15-/-3,10,16-三溴三萘并[3.3.3]丙烷（TBP）和4,7-双（4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基）-2,1,3-苯并噻二唑（BB），并将它们用作双构建单元，通过铃木-宫浦硼化缩聚反应制备了一种多孔共轭微孔聚合物（记为CMP-TBP-BB）。CMP-TBP-BB的合成策略分别利用了TBP中螺旋状三萘并[3.3.3]丙烷部分和BB中苯并噻二唑基团的供体和受体特性。具有螺旋阵列结构单体的CMP不同寻常的二维构象有助于将π组分定位在晶体层中，并建立对齐的传导途径。CMP-TBP-BB表现出出色的荧光特性。利用其独特的二维骨架制备高度对齐的供体-受体构建单元，这通常被认为是一项具有挑战性的任务。这种多孔CMP用作荧光传感器，可选择性且灵敏地检测缺电子硝基炸药和金属硝酸盐。具体而言，CMP-TBP-BB对百万分之一水平的2,4,6-三硝基苯酚和Fe(NO)有响应，其传感特性的实验和理论联合研究结果突出了其作为基于CMP的荧光探针的潜力。此外，由于荧光强度与温度之间具有高线性关系，这种双功能荧光CMP探针表现出显著的温度传感行为，使其成为一种出色的荧光温度计。
