20.500.12556/RUL-138805 Trinuclear magnesium imidazolate borohydride complex A new type of hybrid compound, combining properties of MOFs and borohydrides, was synthesized solvothermally using Mg(BH$_4$)$_2$ and imidazole as precursors. Material in the form of acetonitrile solvate with formula [Mg$_3${(Im)BH$_2$(Im)}$_6$(ImH)$_6$]·CH$_3$CN crystallizes in the space group R$\overline{3}$, having the unit cell parameters a = 15.1942(2) Å and c = 28.3157(3) Å as determined by single crystal X-ray diffraction. The structure was further investigated by solid-state NMR and DFT quantum chemical calculations. The main feature of the structure, reported here for the first time, is a linear trinuclear complex, where octahedrally nitrogen-coordinated Mg$^{2+}$ ions are bridged with {(Im)BH$_2$(Im)}$^−$ units, forming inside voids of 4.6 Å in diameter between the magnesium ions. Polar intermolecular interactions hold the molecules in a dense rhombohedral stacking, where a disordered acetonitrile molecule plays a cohesive role. The compound is stable in air and upon heating to about 160 °C. Using an alternative synthesis method from an imidazole melt, an imidazole solvate with the formula [Mg$_3${(Im)BH$_2$(Im)}$_6$(ImH)$_6$]·ImH and a very similar crystal structure to acetonitrile solvate was prepared. It is stable up to 220 °C. Upon further heating, it transformed into a layered structure with the formula Mg(Im$_3$BH)$_2$, space group P$\overline{3}$1c, and unit cell parameters a = 8.7338(9) Å and c = 17.621(2) Å determined by synchrotron powder diffraction. Besides its structural novelty, two types of potentially reactive hydrogens, bonded to boron and nitrogen in the same molecule, make the material highly interesting for future investigations in the fields of energy storage applications. crystal structure imidazoles ligands molecules solvates kristalna struktura imidazoli ligandi molekule solvati true false true Angleški jezik Slovenski jezik Članek v reviji 2022-08-19 07:22:34 2022-08-19 07:22:34 2022-09-24 04:12:16 0000-00-00 00:00:00 2022 0 0 Str. 12708-12718 iss. 32 Vol. 61 Aug. 2022 0000-00-00 Zaloznikova Objavljeno NiDoloceno 0000-00-00 0000-00-00 0000-00-00 547.8.022 0020-1669 10.1021/acs.inorgchem.2c01319 117494019 acs.inorgchem.2c01319_Trinuclear_Magnesium_Imidazolate_Borohydride_Complex.pdf acs.inorgchem.2c01319_Trinuclear_Magnesium_Imidazolate_Borohydride_Complex.pdf 1 76BD5A745728D4425AD115BED73F3B08 935f80e7bb1b4a2a4e53437c3fd94a16d92634a3ea265c84f8e5ed053ce96cfa fa7b6536-3b26-11ed-9c94-00155dcfd717 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=162055 https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c01319 0 4d58dad5-3587-11ed-92af-00155dcfd717 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=161349 Fakulteta za kemijo in kemijsko tehnologijo 0 0 0