Hybrid materials, in which stable organic radical cations are intercalated into layered inorganic host materials, are of interest since Fujita et al showed the expandability of the used inorganic host lattices as well as a Curie-Weiss behavior in such intercalates.[1] Further investigations on different radical cations in Saponite,[2] Cd1-xPS3,[3] and Somasif[4] showed the ability to control the geometry of the radical arrangement. Thus, such hybrid materials may offer the possibility of inducing cooperative magnetism through strong radical-radical interactions. The presented results will give an overview about the synthesis of inorganic-organic hybrid materials by using synthetic layered clay named Somasif® ME 100 as host lattice and various mono- and di-TEMPO derivatives as well as Nitronyl Nitroxids as organic guest molecules.

However, the main focus of the presented work is on structure determination as well as the detection and quantification of cooperative interactions in such functional materials via magnetic resonance techniques. To gain a deeper understanding of the structure-property correlation we used Solid-State NMR spectroscopy which provides quantifiable structural and analytical results.

In addition, EPR spectroscopy offers complementary information about the local surrounding of the unpaired electrons. With the combined use of these spectroscopic methods, supplemented by X-ray diffraction, vibrational spectroscopy and surface analysis, a generally applicable spectroscopic investigation strategy for complex functional materials was developed.

C.D. acknowledges funding by FAPESP, grant number 2017/06649-0.

[1] W. Fujita, K. Awaga, J. Chem. Soc. Chem. Commun. 1995, 263, 739–740 [2] C. Röben, A. Studer, W. L. Hemme, H. Eckert, Synlett 2010, 1110–1114 [3] W. L. Hemme, W. Fujita, K. Awaga, Solid State NMR, 2011, 39, 106–115 [4] Z. Zeng, D. Matuschek, A. Studer, C. Schwickert, R. Pöttgen, H. Eckert, Dalton, 2013, 42, 8585–8596