NDLI: Structural, electronic and magnetic properties of Cu(ii) complexes of 2-substituted tropones bearing a ferrocenyl group at 5-position

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Dalton Transactions Vol - 39 Issue - 8

Dalton Transactions Vol - 39 Issue - 7

Dalton Transactions Vol - 39 Issue - 6

Dalton Transactions Vol - 39 Issue - 5

Dalton Transactions Vol -0

Structural, electronic and magnetic properties of Cu(ii) complexes of 2-substituted tropones bearing a ferrocenyl group at 5-position

Content Provider	Royal Society of Chemistry (RSC)
Author	Miyake, Yoshihiro Miyasaka, Hitoshi Isomura, Eigo Enoki, Toshiaki Otani, Hiroyuki Nishinaga, Tohru Watanabe, Sayaka Iyoda, Masahiko Aono, Tomoshi Miyazaki, Akira
Copyright Year	2010
Abstract	Heterotrinuclear Fe(II)–Cu(II)–Fe(II) complexes [Cu(FcTropOMe)2(H2O)2](OTf)2 (FcTropOMe = 5-ferrocenyl-2-methoxytropone) (1), [Cu(FcTropNEt2)2](OTf)2 (FcTropNEt2 = 2-(N,N-diethylamino)-5-ferrocenyltropone) (2) and [Cu(FcTropNEt)2] (FcTropNEt = 2-(N-ethylamino)-5-ferrocenyltroponate) (3) were synthesized. In addition, a hexafluorophosphate salt of heterotrinuclear Fe(III)–Cu(II)–Fe(III) complex [Cu(FcTropNEt)2]2+ (32+) was successfully obtained as single crystals by electrochemical oxidation of 3. By comparing the X-ray structures and absorption spectra of dicationic complexes 1 and 2, the 2-(diethylamino)tropone ligand was found to induce a greater intramolecular charge transfer (CT) from ferrocenyl to tropone–Cu(II) moieties than the 2-methoxytropone ligand. On the other hand, 32+ showed a broad CT band in the near-infrared (NIR) region similar to 2, which can be assigned to a transition from troponato–Cu(II) to ferrocenium moieties. As for the magnetic properties of 32+(PF6−)2, measurements of temperature dependence of magnetic susceptibility and ESR on the solid state and in solution revealed the presence of a strong ferromagnetic interaction (JFe–Cu = +12.0 cm−1) between the low spin Fe(III) ion with S = 1/2 and Cu(II) ion with S = 1/2 despite a long distance pathway via the aminotroponato and cyclopentadienyl moieties. DFT calculations supported this intramolecular ferromagnetism, which is induced by a spin polarization mechanism through the π-spacers.
Starting Page	2293
Ending Page	2300
Page Count	8
File Format	HTM / HTML PDF
ISSN	14779226
Volume Number	39
Issue Number	9
Journal	Dalton Transactions
DOI	10.1039/b912255a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	ESR Water of crystallization Hexafluorophosphate Electrochemistry X-ray crystallography Tropone Ligand Ferrocenium tetrafluoroborate Correlation and dependence Magnetic susceptibility Ferromagnetism Ion Cyclopentadienyl
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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