Detrimental Increase of Spin-Phonon Coupling in Molecular Qubits on Substrates.

Molecular qubits are a promising platform for quantum information systems. Although single molecule and ensemble studies have assessed the performance of = 1/2 molecules, it is understood that to function in devices, regular arrays of addressable qubits supported by a substrate are needed. The substrate imposes mechanical and electronic boundary conditions on the molecule; however, the impact of these effects on spin-lattice relaxation times is not well understood.

Effects of a Tridentate Pincer Ligand on Parahydrogen Induced Polarization.

The role of ligands in rhodium- and iridium-catalyzed Parahydrogen Induced Polarization (PHIP) and SABRE (signal amplification by reversible exchange) chemistry has been studied in the benchmark systems, [Rh(diene)(diphos)] and [Ir(NHC)(sub) (H) ] , and shown to have a great impact on the degree of hyperpolarization observed. Here, we examine the role of the flanking moieties in the electron-rich monoanionic bis(carbene) aryl pincer ligand, CCC (Ar=Dipp, 2,6-diisopropyl or Mes, 2,4,6-trimethylphenyl) on the cobalt-catalyzed PHIP and PHIP-IE (PHIP via Insertion and Elimination) chemistry that we have previously reported. The mesityl groups were exchanged for diisopropylphenyl groups to generate the ( CCC)Co(N ) catalyst, which resulted in faster hydrogenation and up to 390-fold H signal enhancements, larger than that of the ( CCC)Co-py (py=pyridine) catalyst.

C NMR Signal Enhancement Using Parahydrogen-Induced Polarization Mediated by a Cobalt Hydrogenation Catalyst.

The use of a cobalt-based catalyst for the generation of hyperpolarized C NMR resonances by parahydrogenation of ethyl acrylate is presented herein. Comparisons of the carboxylate C NMR signal enhancement factor of ethyl propionate between using (CCC)Co-py and a commonly utilized cationic diphosphine rhodium complex demonstrates that the cobalt system is a viable PHIP catalyst alternative. Furthermore, the operative hydrogenation mechanism of the cobalt system was examined by using H, C, and parahydrogen-induced polarization NMR spectroscopies to elucidate reaction intermediates affiliated with the observed H and C NMR signal enhancements in ethyl propionate.