Intermolecular Interaction Tuning of Spin-Crossover Iron(III) Complexes with Aromatic Counteranions

Asami Tsukiashi, Manabu Nakaya, Fumiya Kobayashi, Ryo Ohtani, Masaaki Nakamura, Jack M. Harrowfield, Yang Kim, Shinya Hayami

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48 Citations (Scopus)


Iron(III) spin-crossover (SCO) complexes [Fe(qsal)2]BS·MeOH·H2O (1), [Fe(qsal)2](NS)·MeOH (2), [Fe(qnal)2](NS) (3), and [Fe(qnal)2]PS·MeOH·CH2Cl2 (4) (Hqsal, N-(8-quinolinyl)salicylaldimine; Hqnal, N-(8-quinolinyl)-2-hydroxy-1-naphthaldimine; BS, benzenesulfonate; NS, 1-naphthalenesulfonate; PS, 1-pyrenesulfonate) have been synthesized and characterized by X-ray structure determinations and temperature-dependent magnetic susceptibility measurements. The aromatic counteranions BS, NS, and PS can be used for the tuning of intermolecular coupling through a variety of weak interactions. All of the complexes show temperature-dependent SCO behavior. but the light-induced excited spin-state trapping (LIESST) effect was observed only for 1, 3, and 4 when the samples were illuminated (λ 808 nm) for 1 h at 5 K. In particular, 59% of the LS form of 1 was converted to the metastable HS state by illumination, equal to the highest degree of conversion yet known for LIESST in [Fe(qsal)2]+ derivatives. The lack of a LIESST effect for 2 may be due to the relatively limited degree of interaction between the cations and anions in the lattice, reflected in a much longer minimum Fe···Fe separation in this complex in comparison to the others.

Original languageEnglish
Pages (from-to)2834-2842
Number of pages9
JournalInorganic chemistry
Issue number5
Publication statusPublished - Mar 5 2018
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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