Crystal and molecular structure of poly(1,4-phenyleneazine-N,N-dioxide) (PDNB, 1), obtained from polymerization of 1,4-dinitrosobenzene, is investigated by X-ray powder diffraction (XRPD) and DFT calculations. Starting with the determined crystal structure, we have calculated the electronic structure of the polymer, which reveals that 1 is potentially a wide-bandgap (WBG) semiconductor with a band gap of 2.3 eV. Its calculated electronic spectrum with the absorbance at 400 nm is in good agreement with the experimental data. A highly organized crystal structure with linear chains of polymer indicates possible anisotropic electronic properties that could be useful in molecular photoelectronics (e.g OLEDs). Photolysis of 1 at cryogenic temperatures yields dinitrosobenzene monomers, which re-polymerize at higher temperatures. After this reversible photo-thermal cycle, the starting polymorph of 1 is recovered. Thermal analysis (TG/DSC/DTA) and in situ XRPD measurements show the high thermal stability of 1 until around 150°C.

通过X射线粉末衍射（XRPD）和DFT计算研究了由1,4-二亚硝基苯的聚合反应获得的聚（1,4-亚苯基嗪-N，N-二氧化物）（PDNB，1）的晶体和分子结构。从确定的晶体结构开始，我们计算了聚合物的电子结构，这表明1可能是带隙为2.3 eV的宽带隙（WBG）半导体。其在400 nm处的吸光度计算出的电子光谱与实验数据非常吻合。具有聚合物线性链的高度组织化的晶体结构表明可能在分子光电学中有用的各向异性电子特性（例如OLED）。在低温下1的光解产生二亚硝基苯单体，该亚硝基苯单体在更高的温度下会重新聚合。在该可逆的光热循环之后，回收了1的起始多晶型物。热分析（TG / DSC / DTA）和原位XRPD测量显示，直到150°C左右，其热稳定性均为1。