Akhmedov Tural N, Kumar Ajeet, Starkenburg Daken J, Chesney Kyle J, Abboud Khalil A, Akhmedov Novruz G, Xue Jiangeng, Castellano Ronald K
Department of Chemistry, University of Florida, PO Box 117200, Gainesville, FL, 32611, United States.
Department of Materials Science and Engineering, University of Florida, PO Box 116400, Gainesville, Florida 32611, United States.
Beilstein J Org Chem. 2024 May 8;20:1037-1052. doi: 10.3762/bjoc.20.92. eCollection 2024.
Presented here is the design, synthesis, and study of a variety of novel hydrogen-bonding-capable π-conjugated -heteroacenes, 1,4-dihydropyrazino[2,3-]quinoxaline-2,3-diones (DPQDs). The DPQDs were accessed from the corresponding weakly hydrogen-bonding dicyanopyrazinoquinoxaline (DCPQ) suspensions with excess potassium hydroxide, resulting in moderate to good yields. Both families of compounds were analyzed by UV-vis and NMR spectroscopy, where the consequences of hydrogen bonding capability could be assessed through the structure-property studies. Conversion of the DCPQs into hydrogen-bonding capable DPQDs results in modulation of frontier MO energies, higher molar extinction coefficients, enhanced crystallinity, and on-average higher thermal stability (where in some cases the 5% weight loss temperature is increased by up to 100 °C). Single crystal X-ray diffraction data could be obtained for three DPQDs. One reveals pairwise hydrogen bonding in the solid state as well as a herringbone packing arrangement rendering it a promising candidate for additional studies in the context of organic optoelectronic devices.
本文介绍了多种具有氢键作用的新型π共轭杂并四苯——1,4-二氢吡嗪并[2,3 - ]喹喔啉-2,3 - 二酮(DPQDs)的设计、合成及研究。通过用过量氢氧化钾处理相应的弱氢键二氰基吡嗪并喹喔啉(DCPQ)悬浮液来制备DPQDs,产率适中至良好。这两类化合物均通过紫外可见光谱和核磁共振光谱进行分析,通过结构-性质研究可以评估氢键作用的影响。将DCPQs转化为具有氢键作用的DPQDs会导致前沿分子轨道能量的调制、更高的摩尔消光系数、增强的结晶度以及平均而言更高的热稳定性(在某些情况下,5%失重温度提高了高达100℃)。获得了三种DPQDs的单晶X射线衍射数据。其中一个显示了固态中的成对氢键以及人字形堆积排列,使其成为有机光电器件背景下进一步研究的有前途的候选物。