For further studies, crystalline samples of 2 obtained by route 1 were used.
In addition, a diffractogram simulated for 2 from single-crystal X-ray data and after removal of solvent molecules shows a good match with the experimental PXRD patterns ( Figure 1).
The presence of different solvent molecules in the crystal lattice does not change the PXRD patterns of the 2 and 2′ samples obtained via routes 1 and 2. The present study provides a unique example of an MOF that is assembled from two different types of adamantoid Cu 4 and PTA═O cages, thus contributing to widening a diversity of functional metal–organic frameworks. This copper(II) compound also acts as an active catalyst for the mild oxidation and carboxylation of alkanes. The magnitude of exchange coupling, predicted from the broken-symmetry DFT studies, is in good agreement with the experimental data. Single-point DFT calculations disclose a strong delocalization of the spin density over the tetranuclear unit. Magnetic susceptibility measurements on this MOF in the temperature range of 1.8–300 K reveal a ferromagnetic interaction ( J = +20 cm –1) between the neighboring copper(II) ions.
The obtained product is composed of diamandoid tetracopper(II) cages and monocopper(II) units that are assembled, via the diamandoid μ-PTA═O linkers, into an intricate 3D net with an nbo topology. This work describes an unexpected generation of a new 3D metal–organic framework (MOF), n♲ nCl-EtOH♲.5 nH 2O, from copper(II) chloride and 1,3,5-triaza-7-phosphaadamantane 7-oxide (PTA═O).
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