Warneke Jonas, Samayoa-Oviedo Hugo Y, Rohdenburg Markus, Li Xilai, Knorke Harald, Laskin Julia
Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Leipzig, Germany.
Leibniz Institute of Surface Engineering (IOM), Leipzig, Germany.
Nat Rev Chem. 2025 May 29. doi: 10.1038/s41570-025-00719-1.
Chemists often treat gaseous fragment ions as esoteric chemical species of interest to only analytical mass spectrometry and gas-phase ion chemistry. However, their potential as building blocks for designing new compounds in the condensed phase is largely unexplored. Developments in preparative mass spectrometry instrumentation have opened up a new research field focused on understanding the chemistry of well-defined gaseous fragment ions on surfaces. In this Review, we highlight the preparative potential of gaseous fragment ions for synthesizing new compounds in the condensed phase. We discuss factors affecting the selectivity of the observed reactivity of fragment ions, examine the effect of charge on reaction mechanisms, and introduce the unexpected reactivity of ions of the same polarity on surfaces in the absence of solvent molecules. These developments hold the potential to transform preparative mass spectrometry into a valuable method for small-scale chemical synthesis in almost all fields of molecular sciences.
化学家们常常将气态碎片离子视为只有分析质谱和气相离子化学领域感兴趣的深奥化学物种。然而，它们作为在凝聚相中设计新化合物的构建单元的潜力在很大程度上尚未得到探索。制备型质谱仪器的发展开辟了一个新的研究领域，该领域专注于理解在表面上明确的气态碎片离子的化学性质。在本综述中，我们强调气态碎片离子在凝聚相中合成新化合物的制备潜力。我们讨论影响碎片离子所观察到的反应性选择性的因素，研究电荷对反应机理的影响，并介绍在没有溶剂分子的情况下相同极性的离子在表面上的意外反应性。这些进展有可能将制备型质谱转变为分子科学几乎所有领域中小规模化学合成的一种有价值的方法。
