Breathing crystals based on polymer-chain complexes of Cu(hfac)(2) with nitroxides exhibit thermally and light-induced magnetostructural anomalies in many aspects similar to a spin crossover. In the present work, we report the synthesis and investigation of a new family of Cu(hfac)(2) complexes with tert-butylpyrazolylnitroxides and their nonradical structural analogues. The complexes with paramagnetic ligands clearly exhibit structural rearrangements in the copper(II) coordination units and accompanying magnetic phenomena characteristic for breathing crystals. Contrary to that, their structural analogues with diamagnetic ligands do not undergo rearrangements in the copper(II) coordination environments. This confirms experimentally the crucial role of paramagnetic ligands and exchange interactions between them and copper(II) ions for the origin of magnetostructural anomalies in this family of molecular magnets.
Breathing crystals based on polymer-chain complexes of Cu(hfac)2 (hfac = hexafluoroacetylacetonate) with nitronyl nitroxides represent a new type of molecular magnetic sensors, exhibiting thermally and light-induced structural rearrangements in the spin clusters Cu ← (O∸N<)n accompanied by magnetic anomalies. To shed light on the driving forces of the rearrangements a method for the synthesis of sterically hindered 4-oxo-3,4-dihydro-2H-pyrrole-N-oxides (nitronyl ketones) structurally mimicking nitronyl nitroxides in breathing crystals has been determined. This method employs palladium-catalyzed cross-coupling of 3,3,4-trimethyl-4-nitropentanoic acid chloride with 4-stannylpyrazoles, leading to the formation of nitroketones followed by soft reduction into hydroxylamines, that then undergo self-initiated cyclization into the corresponding nitrones. The radical oxidation of the latter finally yields the target nitronyl ketones. An X-ray diffraction analysis of the nitronyl ketones confirms that their structural characteristics are close to those of the corresponding nitronyl nitroxides. Moreover, upon reaction with Cu(hfac)2, diamagnetic nitronyl ketones form polymer-chain complexes with a ‘head-to-tail’ motif and a structure similar to their analogues containing paramagnetic nitronyl nitroxides. Finally, it has been found that one of the complexes with nitronyl ketones does manifest a purely structural phase transition similar to its copper-nitroxide analogue, but at the same time it does not manifest any signs of a magneto-structural transition characteristic for breathing crystals where a Jahn–Teller axis in the coordination units CuNO4(O∸N<) is flipped. This observation strongly confirms the crucial role of the exchange interactions between spins of copper and nitroxide for the origin of magneto-structural anomalies in breathing crystals.
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