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Tailoring the structures and transformations between copper complexes in gas–solid reactions and solid-state synthesis

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Abstract

In this study, two copper(II) salts with different configurations, 2[H3LCuCl4][Cu2Cl6] (1) and [H4L][CuCl4]2Cl (2) (L = (1R,2R)-N,N′-bis(pyridin-4-ylmethyl)cyclohexane-1,2-diamine), have been synthesized and applied in the following solid–gas and solid–solid reactions. Both salts 1 and 2 gave rise to the salt ([H4L][Cu2Cl8]H2O (3) upon exposure to HCl gas or grinding with equal moles of CuCl2·2H2O. In the reaction from 1 to 3, the Cu–N coordination bond of [H3LCuCl4]+ in 1 was broken by the hydrated vapours of HCl and new N–H, Cu–Cl–Cu and Cu-H2O bonds of mixture products 3 and [H4L][CuCl3(H2O)]3Cl (4) were generated. In the reaction from 2 to 3, a stoichiometric ratio-controlled transformation occurred with the change in the geometry of copper(II) anions from [CuCl4]2− to [Cu2Cl8]4−. The detailed structural changes between covalent and coordination bonds and the transformations of these copper complexes are described in the paper, which has provided a good model for understanding the reaction pathways and insight into the structural transformation of materials of interest. Recrystallization of the grinding product of the ligand L with CuCl2·2H2O obtained a novel coordination polymer ([Cu2(L′)2Cl3]Cl)n (5, L′ = (1R,2R)-N-(pyridin-4-ylmethyl)cyclohexane-1,2-diamine) with a clear channel of the pore size being 16 × 13 Å, which is accessible to chloride anions and water molecules and shows a good adsorption performance on dyes and I2 ethanol solutions.

Graphical abstract: Tailoring the structures and transformations between copper complexes in gas–solid reactions and solid-state synthesis

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Article information


Submitted
15 Jul 2020
Accepted
23 Sep 2020
First published
24 Sep 2020

Inorg. Chem. Front., 2020, Advance Article
Article type
Research Article

Tailoring the structures and transformations between copper complexes in gas–solid reactions and solid-state synthesis

H. Li, R. Li and F. Guo, Inorg. Chem. Front., 2020, Advance Article , DOI: 10.1039/D0QI00850H

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