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Issue 29, 2019
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Anion tuning of Zn2+ architectures using a Tris-base salicylic ligand

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Abstract

In this study, a hydroxyl-rich Schiff base ligand, H4L, and its resulting complexes with ZnCl2, Zn(CH3COO)2 and Zn(ClO4)2 were explored. Interestingly, depending on the zinc salt and/or the crystallisation method, four unique structures were obtained. A synthesis with ZnCl2 gave 1, a mononuclear structure ((H3L)2Zn), while with Zn(CH3COO)2, a trinuclear system [(H3L)2Zn3(CH3COO)4], 2, was found. Interestingly two multinuclear architectures were observed with Zn(ClO4)2. Firstly, diethyl ether diffusion of a methanolic reaction mixture with minimal atmospheric air volume gave 3, a hexanuclear architecture of the type [(H2L)4(H3L)2Zn6](ClO4)2, while slow evaporation of a similar mixture gave 4, a nonanuclear architecture with the formula [(H2L)6Zn9(CO3)2](ClO4)2. Compound 4 unexpectedly fixed atmospheric CO2 as CO32−, incorporating it into the architecture. As expected, a diethyl ether diffusion with a larger volume of air (∼100 mL) of a similar methanolic reaction mixture gave a mixture of 3 and 4. In addition, bulk samples of all compounds were also investigated by PXRD, and results are in good agreement with the observed single crystal data. Furthermore, complexes 1–4 were characterised using FT-IR and simultaneous thermal analysis (STA), and additionally the photophysical properties of H4L and complexes 1–4 have also been explored.

Graphical abstract: Anion tuning of Zn2+ architectures using a Tris-base salicylic ligand

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Supplementary files

Article information


Submitted
15 May 2019
Accepted
28 May 2019
First published
29 May 2019

CrystEngComm, 2019,21, 4267-4274
Article type
Paper

Anion tuning of Zn2+ architectures using a Tris-base salicylic ligand

D. J. Fanna, A. R. Craze, I. Etchells, S. Bhattacharyya, J. K. Clegg, E. G. Moore, C. E. Marjo, A. Trinchi, G. Wei, J. K. Reynolds and F. Li, CrystEngComm, 2019, 21, 4267
DOI: 10.1039/C9CE00749K

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