Effect of the Diamagnetic Single-Crystalline Host on the Angular-Resolved Electron Nuclear Double Resonance Experiments: Case of Paramagnetic [BuN][Cu(opba)] Embedded in Diamagnetic [BuN][Ni(opba)].

The electron spin resonance (ESR) and electron nuclear double resonance (ENDOR) spectroscopies are frequently used to determine hyperfine () and quadrupole () tensors for the paramagnetic transition-metal complexes, which knowledge enables estimation of the spin density distribution in the complex and the assessment of magnetic exchange pathways in polynuclear molecular networks. The most accurate results can be obtained if paramagnetic complexes are isolated in a single-crystalline diamagnetic host. In this work we were able to detect angle-resolved ESR/ENDOR spectra of the paramagnetic [BuN][Cu(opba)] (opba = -phenylenebis(oxamato) complex hosted by the single crystal of diamagnetic [BuN][Ni(opba)], which allow recovery of , , and -tensors, all at once. Remarkably, with the aid of theoretical modeling, our data have unveiled the effect of multipositional hosting of the paramagnetic complex in the diamagnetic matrix. This effect can have a profound influence on the data handling and must be carefully considered while interpreting similar experiments.