Combination of illumination and high resolution NMR spectroscopy: Key features and practical aspects, photochemical applications, and new concepts

In the last decade, photochemical and photocatalytic applications have developed into one of the dominant research fields in chemistry. However, mechanistic investigations to sustain this enormous progress are still relatively sparse and in high demand by the photochemistry community. UV/Vis spectroscopy and EPR spectroscopy have been the main spectroscopic tools to study the mechanisms of photoreactions due to their higher time resolution and sensitivity. On the other hand, application of NMR in photosystems has been mainly restricted to photo-CIDNP, since the initial photoexcitation was thought to be the single key to understand photoinduced reactions. In 2015 the Gschwind group showcased the possibility that different reaction pathways could occur from the same photoexcited state depending on the reaction conditions by using in situ LED illumination NMR. This was the starting point to push the active participation of NMR in photosystems to its full potential, including reaction profiling, structure determination of intermediates, downstream mechanistic studies, dark pathways, intermediate sequencing with CEST etc. Following this, multiple studies using in situ illumination NMR have been reported focusing on mechanistic investigations in photocatalysis, photoswitches, and polymerizations. The recent increased popularity of this technique can be attributed to the simplicity of the experimental setup and the availability of low cost, high power LEDs. Here, we review the development of experimental design, applications and new concepts of illuminated NMR. In the first part, we describe the development of different designs of NMR illumination apparatus, illuminating from the bottom/side/top/inside, and discuss their pros and cons for specific applications. Furthermore, we address LASERs and LEDs as different light sources as well as special cases such as UVNMR(-illumination), FlowNMR, NMR on a Chip etc. To complete the discussion on experimental apparatus, the advantages and disadvantages of in situ LED illumination NMR versus ex situ illumination NMR are described. The second part of this review discusses different facets of applications of inside illumination experiments. It highlights newly revealed mechanistic and structural information and ideas in the fields of photocatalyis, photoswitches and photopolymerization. Finally, we present new concepts and methods based on the combination of NMR and illumination such as sensitivity enhancement, chemical pump probes, experimental access to transition state combinations and NMR actinometry. Overall this review presents NMR spectroscopy as a complementary tool to UV/Vis spectroscopy in mechanistic and structural investigations of photochemical processes. The review is presented in a way that is intended to assist the photochemistry and photocatalysis community in adopting and understanding this astonishingly powerful in situ LED illumination NMR method for their investigations on a daily basis.