The structures of ordered defects in thiocyanate analogues of Prussian Blue

Cliffe, Matthew J.; Keyzer, Evan N.; Bond, Andrew D.; Astle, Maxwell A.; Grey, Clare P.

doi:10.1039/d0sc01246g

The structures of ordered defects in thiocyanate analogues of Prussian Blue

Journal Article · Thu Apr 09 00:00:00 EDT 2020 · Chemical Science

DOI:https://doi.org/10.1039/d0sc01246g· OSTI ID:1816886

^[1]; Keyzer, Evan N. ^[2]; ^[2]; ^[3]; Grey, Clare P. ^[2]

Univ. of Cambridge (United Kingdom). Dept. of Chemistry; Univ. of Nottingham (United Kingdom). School of Chemistry; OSTI
Univ. of Cambridge (United Kingdom). Dept. of Chemistry
Univ. of Nottingham (United Kingdom). School of Chemistry

We report the structures of six new divalent transition metal hexathiocyanatobismuthate frameworks with the generic formula $$\Big\{ M[Bi(SCN)_6]_\frac{2+x}{3} \Big\}$$ $$\{guest\}^{x+}$$, M = Mn, Co, Ni and Zn. These frameworks are defective analogues of the perovskite-derived trivalent transition metal hexathiocyanatobismuthates M^III[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)₆^3- vacancies, M_Bi 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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1816886

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 17 Vol. 11; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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The structures of ordered defects in thiocyanate analogues of Prussian Blue

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