Symmetry breaking of parahydrogen using iridium catalysts converts singlet spin order into observable hyperpolarization. In this contribution, iridium catalysts are designed to exhibit asymmetry in their hydrides, regulated by in situ generation of deuterated ammonia governed by ammonium buffers. The concentrations of ammonia (N) and pyridine (P) provide a handle to generate a variety of stereo‐chemically asymmetric N‐heterocyclic carbene iridium complexes, ligating either [3xP], [2xP;N], [P;2xN] or [3xN] in an octahedral SABRE type configuration. The non‐equivalent hydride positions, in correspondence with the ammonium buffer solutions, enables to extend singlet‐triplet or S⟩→|T0⟩ mixing at high magnetic field and experimentally induce prolonged generation of non‐equilibrium longitudinal two‐spin order. This long‐lasting magnetization can be exploited in hyperpolarized 2D‐OPSY‐COSY experiments providing direct structural information on the catalyst using a single contact with parahydrogen. Separately, field cycling revealed hyperpolarization properties in low‐field conditions. Controlling catalyst stereochemistry by introducing small and deuterated ligands, such as deuterated ammonia, simplifies the spin‐system. This is shown to unify experimental and theoretically derived field‐sweep experiments for four‐spin systems.

The front cover artwork front cover artwork is provided by NMRCoRe, the Flemish NMR/X‐Ray platform for Convergence Research and was designed by Ir. Ewoud Vaneeckhaute and Dr. Eric Breynaert. The image shows the reciprocity between parahydrogen, deuterated ammonia and iridium allowing for hyperpolarized 2D NMR via long‐term availability of longitudinal spin order. Read the full text of the Article at 10.1002/cphc.202100079.

The Front Cover The image shows the reciprocity between parahydrogen, deuterated ammonia and iridium allowing for hyperpolarized 2D NMR via long‐term availability of longitudinal spin order. More information can be found in the Article by Eric Breynaert and co‐workers.