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Carboxylic acid functionalized spin-crossover iron(II) grids for tunable switching and hybrid electrode fabrication

Shiga, Takuya; Sato, Yamato; Tachibana, Minami; Sato, Hiroki; Matsumoto, Takuto; Sagayama, Hajime; Kumai, Reiji; Murakami, Youichi; Newton, Graham N.; Oshio, Hiroki


Takuya Shiga

Yamato Sato

Minami Tachibana

Hiroki Sato

Takuto Matsumoto

Hajime Sagayama

Reiji Kumai

Youichi Murakami

Hiroki Oshio


Two carboxyl-substituted iron(II) grids, one protonated, [Fe4(HL)4](BF4)4·4MeCN·AcOEt (1), and the other deprotonated, [Fe4(L)4]·DMSO·EtOH (2), where H2L = 4-{4,5-bis[6-(3,5-dimethylpyrazol-1-yl)pyrid-2-yl]-1H-imidazol-2-yl}benzoic acid, were synthesized. Single-crystal X-ray structure analyses reveal that both complexes have a tetranuclear [2 × 2] grid structure. 1 formed one-dimensional chains through intermolecular hydrogen bonds between the carboxylic acid units of neighboring grids, while 2 formed two-dimensional layers stabilized by π–π-stacking interactions. 1 showed spin transition between the 3HS-1LS and 1.5HS-2.5LS states around 200 K, while 2 showed spin-crossover between the 4LS and 2LS-2HS states above 300 K. A modified indium–tin oxide (ITO) electrode was fabricated by soaking the ITO in a solution of 1. The resultant electrode showed reversible redox waves attributed to the original redox processes of iron(II)/iron(III).


Shiga, T., Sato, Y., Tachibana, M., Sato, H., Matsumoto, T., Sagayama, H., …Oshio, H. (2018). Carboxylic acid functionalized spin-crossover iron(II) grids for tunable switching and hybrid electrode fabrication. Inorganic Chemistry, 57(22), 14013-14017.

Journal Article Type Article
Acceptance Date Oct 26, 2018
Online Publication Date Oct 31, 2018
Publication Date Oct 31, 2018
Deposit Date Nov 8, 2018
Publicly Available Date Nov 1, 2019
Journal Inorganic Chemistry
Print ISSN 0020-1669
Electronic ISSN 1520-510X
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 57
Issue 22
Pages 14013-14017
Keywords Spin crossover; Magnetism; Switchable molecules; Iron; Polynuclear complex
Public URL
Publisher URL
Additional Information This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Inorganic Chemistry, copyright © American Chemical Society after peer review. To access the final edited and published work see


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