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Published March 28, 2019 | Supplemental Material + Published
Journal Article Open

Tuning the formal potential of ferrocyanide over a 2.1 V range


We report the synthesis and characterization of homoleptic borane adducts of hexacyanoferrate(II). Borane coordination blueshifts d–d transitions and CN IR and Raman frequencies. Control over redox properties is established with respect to borane Lewis acidity, reflected in peak anodic potential shifts per borane of +250 mV for BPh_3 and +350 mV for B(C_6F_5)_3. Electron transfer from [Fe(CN-B(C_6F_5)_3)_6]^(4−) to photogenerated [Ru(2,2′-bipyridine)_3]^(3+) is very rapid, consistent with voltammetry data. Coordination by Lewis acids provides an avenue for selective modification of the electronic structures and electrochemical properties of cyanometalates.

Additional Information

© 2019 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. The article was received on 08 Nov 2018, accepted on 17 Feb 2019 and first published on 21 Feb 2019. The authors thank Mike Gray and Kimberly See for help in collecting solid-state Raman data. Mike Takase and Larry Henling provided invaluable assistance in collecting and refining X-ray crystallographic data. The authors also thank Brian Sanders and Wesley Kramer for helpful discussions. Supported by NSF (CCI CHE-1305124) and (CHE-1763429). Additional support was provided by the Arnold and Mabel Beckman Foundation. There are no conflicts to declare.

Attached Files

Published - c8sc04972f.pdf

Supplemental Material - c8sc04972f1_si.pdf

Supplemental Material - c8sc04972f2.cif


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