Since external magnetic fields were first employed to deflect paramagnetic atoms in 1921, a range of magnetic field–based methods have been introduced to state-selectively manipulate paramagnetic species. These methods include magnetic guides, which selectively filter paramagnetic species from all other components of a beam, and magnetic traps, where paramagnetic species can be spatially confined for extended periods of time. However, many of these techniques were developed for atomic—rather than molecular—paramagnetic species. It has proven challenging to apply some of these experimental methods developed for atoms to paramagnetic molecules. Thanks to the emergence of new experimental approaches and new combinations of existing techniques, the past decade has seen significant progress toward the manipulation and control of paramagnetic molecules. This review identifies the key methods that have been implemented for the state-selective manipulation of paramagnetic molecules—discussing the motivation, state of the art, and future prospects of the field. Key applications include the ability to control chemical interactions, undertake precise spectroscopic measurements, and challenge our understanding of chemical reactivity at a fundamental level.

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