Solid-state grinding plays a very important role in the study of the dynamics changes of a reaction, especially as a means of selectively preparing specific stoichiometric crystalline supramolecular complexes or cocrystals. Herein, using the tetradentate ligand (1R,2R)-N,N′-bis(pyridin-4-ylmethyl)cyclohexane-1,2-diamine (L), two copper(ii) chloride salts, namely [H4L]4+·[CuCl3(H2O)]-·3Cl- (1) and [H4L]4+·[Cu2Cl8]4-·H2O (2), were produced via 1:1 and 1:2 stoichiometric controlled synthesis in a two-step process by grinding the reactants together using a mortar and pestle. By adding appropriate amounts of the corresponding components, the reversible transformation of the two salts occurred. The progress of the reversible reaction between the salt 1 and 2 was dynamically monitored by fluorescence spectroscopy, powder X-ray diffraction and Raman spectroscopy. Quantum-mechanical (QM) calculations specific for crystalline solid phases provided some insights into the relative stabilities of the two salts, indicating plausible driving forces for the reversible transformation.
Stoichiometry mechanosynthesis and interconversion of metal salts containing [CuCl3(H2O)]- and [Cu2Cl8]4-
Famulari A.;
2019-01-01
Abstract
Solid-state grinding plays a very important role in the study of the dynamics changes of a reaction, especially as a means of selectively preparing specific stoichiometric crystalline supramolecular complexes or cocrystals. Herein, using the tetradentate ligand (1R,2R)-N,N′-bis(pyridin-4-ylmethyl)cyclohexane-1,2-diamine (L), two copper(ii) chloride salts, namely [H4L]4+·[CuCl3(H2O)]-·3Cl- (1) and [H4L]4+·[Cu2Cl8]4-·H2O (2), were produced via 1:1 and 1:2 stoichiometric controlled synthesis in a two-step process by grinding the reactants together using a mortar and pestle. By adding appropriate amounts of the corresponding components, the reversible transformation of the two salts occurred. The progress of the reversible reaction between the salt 1 and 2 was dynamically monitored by fluorescence spectroscopy, powder X-ray diffraction and Raman spectroscopy. Quantum-mechanical (QM) calculations specific for crystalline solid phases provided some insights into the relative stabilities of the two salts, indicating plausible driving forces for the reversible transformation.File | Dimensione | Formato | |
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