Solution-phase electrochemistry-nuclear magnetic resonance of small organic molecules

•Critical review of electrochemistry coupled to nuclear magnetic resonance (EC-NMR).•We discuss strategies, instrumentation and applications of EC-NMR.•Miniaturized NMR probes and miniaturized EC-NMR section•We give outlook on possible future developments in EC-NMR.

The hyphenation of electrochemistry and solution-phase nuclear magnetic resonance spectrometry (EC-NMR) has made significant progress in several areas:•dedicated NMR probes integrating the electrodes with minimal impact on spectral quality;•different strategies regarding the relative placement of electrodes versus magnet/radiofrequency coils;•solutions in aspects of the hyphenation, such as noise reduction strategies or 1H NMR silent electrolytes;•applications, e.g., studies of oxidative metabolism and electronic polymers.Because EC-NMR has moved from sporadic reports to systematic investigation in this decade, we summarize the developments in this nascent field. We focus on aspects related to hyphenation and highlight applications and a newer development: miniaturized EC-NMR.EC-NMR should become increasingly valuable for fundamental and applied studies related to electrochemical reactions, partly because it is highly complementary to other techniques, such as EC-electron spin-resonance spectrometry and EC-mass spectrometry.