Issue 17, 2020

The structures of ordered defects in thiocyanate analogues of Prussian Blue

Abstract

We report the structures of six new divalent transition metal hexathiocyanatobismuthate frameworks with the generic formula Image ID:d0sc01246g-t2.gif, M = Mn, Co, Ni and Zn. These frameworks are defective analogues of the perovskite-derived trivalent transition metal hexathiocyanatobismuthates MIII[Bi(SCN)6]. The defects in these new thiocyanate frameworks order and produce complex superstructures due to the low symmetry of the parent structure, in contrast to the related and more well-studied cyanide Prussian Blue analogues. Despite the close similarities in the chemistries of these four transition metal cations, we find that each framework contains a different mechanism for accommodating the lowered transition metal charge, making use of some combination of Bi(SCN)63− vacancies, MBi antisite defects, water substitution for thiocyanate, adventitious extra-framework cations and reduced metal coordination number. These materials provide an unusually clear view of defects in molecular framework materials and their variety suggests that similar richness may be waiting to be uncovered in other hybrid perovskite frameworks.

Graphical abstract: The structures of ordered defects in thiocyanate analogues of Prussian Blue

Supplementary files

Article information

Article type
Edge Article
Submitted
28 Feb 2020
Accepted
08 Apr 2020
First published
09 Apr 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2020,11, 4430-4438

The structures of ordered defects in thiocyanate analogues of Prussian Blue

M. J. Cliffe, E. N. Keyzer, A. D. Bond, M. A. Astle and C. P. Grey, Chem. Sci., 2020, 11, 4430 DOI: 10.1039/D0SC01246G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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