Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou 515063, China.
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong 999077, China.
J Phys Chem Lett. 2022 Jul 21;13(28):6571-6579. doi: 10.1021/acs.jpclett.2c01037. Epub 2022 Jul 14.
Developing a suitable initiation for the energetic materials that respond to a low-power near-infrared laser can aid in replacing the current expensive and bulky laser-initiation systems. Here, we report on a system of molecularly tailored 1:1 donor-acceptor (D-A) charge-transfer (CT) cocrystals that manifest ultrabroad absorption (200-2500 nm) characteristics as well as noteworthy very fast self-assembly behaviors. The very narrow highest occupied molecular orbital-lowest unoccupied molecular orbital gap enables ,,','-tetramethyl--phenylenediamine and tetrahalo-1,4-benzoquinones (TMPD-TXBQ) cocrystals to have a great light-harvesting ability in the near-infrared range. When irradiated with a low-power hand-held 808 nm laser with an input energy of only 40 mJ or a power density of 260 mW·cm, these TMPD-TXBQ cocrystals immediately undergo an efficient photothermal conversion followed by a dramatic exothermic thermal polymerization reaction due to the face-to-face D-A-D-A stacking in these cocystals to achieve a temperature as high as 318.9 °C. This temperature is high enough for a thermal initiation of most common energetic materials, and thus this TMPD-TXBQ cocrystal can potentially act as a near-infrared laser initiator that is compact, lightweight, and cost-effective.
开发对低功率近红外激光有响应的能量材料的合适引发剂,可以帮助取代当前昂贵且庞大的激光引发系统。在这里,我们报告了一种分子裁剪的 1:1 给体-受体(D-A)电荷转移(CT)共晶的体系,该体系表现出超宽的吸收(200-2500nm)特性以及显著的非常快速的自组装行为。非常窄的最高占据分子轨道-最低未占据分子轨道间隙使,,','-四甲基--对苯二胺和四卤代-1,4-苯醌(TMPD-TXBQ)共晶在近红外范围内具有很强的光捕获能力。当用低功率手持式 808nm 激光照射时,输入能量仅为 40mJ 或功率密度为 260mW·cm,这些 TMPD-TXBQ 共晶由于共晶中面对面的 D-A-D-A 堆积而立即经历有效的光热转换,随后发生剧烈的放热热聚合反应,从而达到 318.9°C 的高温。这个温度足以引发大多数常见的能量材料的热引发,因此这种 TMPD-TXBQ 共晶可以作为一种紧凑、轻巧且具有成本效益的近红外激光引发剂。