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The Structures of Ordered Defects in Thiocyanate Analogues of Prussian Blue

Cliffe, Matthew; Keyzer, Evan; Bond, Andrew; Astle, Maxwell A.; Grey, Clare


Evan Keyzer

Andrew Bond

Maxwell A. Astle

Clare Grey


We report the structures of six new divalent transition metal hexathiocyanatobismuthate frame-
works with the generic formula {M[Bi(SCN)6]2+x }x− {guest}x+, M = Mn, Co, Ni and Zn. These 3 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) 3– vacancies, M 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.


Cliffe, M., Keyzer, E., Bond, A., Astle, M. A., & Grey, C. (2020). The Structures of Ordered Defects in Thiocyanate Analogues of Prussian Blue. Chemical Science, 11(17), 4430-4438.

Journal Article Type Article
Acceptance Date Apr 8, 2020
Online Publication Date Apr 9, 2020
Publication Date May 7, 2020
Deposit Date Aug 10, 2020
Publicly Available Date Aug 13, 2020
Journal Chemical Science
Print ISSN 2041-6520
Electronic ISSN 2041-6539
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 11
Issue 17
Pages 4430-4438
Public URL
Publisher URL!divAbstract


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