Experimental strategies for 13C–15N dipolar NMR spectroscopy in liquid crystals at the natural isotopic abundance

Abstract

Direct dipolar spin couplings are informative and sensitive probes for a wide range of dynamic processes and structural properties at atomic, molecular and supramolecular levels in liquid crystals and other anisotropic materials. Usually, heteronuclear ¹³C–¹H dipolar couplings in liquid crystals with natural ¹³C abundance are measured. Recording ¹³C–¹⁵N NMR dipolar spectra in unlabeled materials is challenging because of the unfavorable combination of two rare isotopes. Here we design and compare various experimental strategies to measure short- and long-range heteronuclear ¹³C–¹⁵N dipolar couplings in liquid crystalline samples with high molecular orientational order. New techniques were developed to record ¹³C and ¹⁵N spectra of naturally occurring ¹³C–¹⁵N spin pairs with increased signal intensity and spectral resolution while suppressing the signals of the uncoupled isotopes. Highly resolved ¹³C–¹⁵N dipolar spectra were recorded within an experimental time of a few hours. Coupling constants in a broad range of 10–1000 Hz between spins separated by up to five chemical bonds and distances of up to 5 Å were measured. Because of their relatively low demands on radio-frequency power levels, the experiments were easy to implement using conventional high-resolution solution-state NMR hardware. Experimental data were compared to the results of density functional theory and molecular dynamics computational analyses. The presented experimental methods to characterize the dipolar couplings in unlabeled materials provide novel routes to investigate molecular structure and dynamics in mesophases.