2-Bromo-1-(3,3-二硝基氮杂环丁烷-1-基)乙烷-1-酮 (RRx-001) 是一种缺氧细胞化疗药物，已在放化疗联合治疗中显示出协同作用。该化合物与在辐射的物理化学阶段形成的大量次级低能电子的相互作用可能导致这些协同效应。本研究重点关注 RRx-001 与低能电子相互作用的第一步，其中形成并碎裂瞬态阴离子。两个实验的结合使我们能够解开 RRx-001 阴离子在不同时间尺度上的衰变。电子的单独存在引发NO2和HNO2中性离子的快速解离，而NO2-和Br-阴离子则直接或通过中间复合物产生。基于我们的量子化学计算，我们提出 π*(NO2) 和 σ*(C-Br) 态之间的双向系间跨越解释了实验光谱。监测的快速动态也会影响阴离子的凝聚相化学。© 2024 Wiley‐VCH GmbH。

2-Bromo-1-(3,3-dinitroazetidin-1-yl)ethan-1-one (RRx-001) is a hypoxic cell chemotherapeutics with already demonstrated synergism in combined chemo-radiation therapy. The interaction of the compound with secondary low-energy electrons formed in large amounts during the physico-chemical phase of the irradiation may lead to these synergistic effects. The present study focuses on the first step of RRx-001 interaction with low-energy electrons in which a transient anion is formed and fragmented. Combination of two experiments allows us to disentangle the decay of the RRx-001 anion on different timescales. Sole presence of the electron initiates rapid dissociation of NO2 and HNO2 neutrals while NO2- and Br- anions are produced both directly and via intermediate complexes. Based on our quantum chemical calculations, we propose that bidirectional intersystem crossing between π*(NO2) and σ*(C-Br) states explains the experimental spectra. The fast dynamics monitored will impact the condensed phase chemistry of the anion as well.© 2024 Wiley‐VCH GmbH.