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Charge-transfer salts of methylferrocenes with DCNQI derivatives (DCNQI = N,N′-dicyano-1,4-benzoquinonediimine): Crystal structures and magnetic properties
Authors:Yusuke Funasako  Takahiro Sakurai
Institution:a Department of Chemistry, Graduate School of Science, Kobe University, Rokkodai, Nada, Hyogo 657-8501, Japan
b Center for Supports to Research and Education Activities, Kobe University, Rokkodai, Nada, Hyogo 657-8501, Japan
c Molecular Photoscience Research Center, Kobe University, Rokkodai, Nada, Hyogo 657-8501, Japan
Abstract:Organometallic charge-transfer salts composed of decamethyl-, octamethyl-, and dimethylferrocene with N,N′-dicyano-1,4-benzoquinonediimine (DCNQI) derivatives were prepared. Fe(C5Me5)2](MeO)2DCNQI] (1) and Fe(C5Me4H)2]Me2DCNQI] (2) were 1:1 DA salts with mixed-stack structures, whereas Fe(C5Me4H)2](MeO)2DCNQI]2 (3) and Fe(C5MeH4)2]DCNQI]2 (4) were 1:2 DA salts. 3 exhibited a segregated-stack structure, in which charge separation was observed in the acceptor column. 1 became a metamagnet below TN = 5.0 K, whereas the other salts were paramagnets. Valence states and charge-transfer (CT) transitions in these complexes are discussed based on the neutral-ionic (NI) phase diagram.
Keywords:Crystal structures  Magnetic properties  Charge-transfer complex  Ferrocene  DCNQI
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