title: Design of novel inorganic-organic hybrid materials based on iron-chloranilate mononuclear complexes: characteristics of hydrogen-bond-supported layers toward the intercalation of guests.
abstract: Novel intercalation compounds constructed from the common two-dimensional hydrogen-bond-supported layers and functional guests [(H(0.5)phz)(2)[Fe(CA)(2)(H(2)O)(2)].2H(2)O](n)(1), ([Fe(Cp)(2)][Fe(CA)(2)(H(2)O)(2)])(n)(2), ([Fe(Cp*)(2)][Fe(CA)(2)(H(2)O)(2)])(n)(3), and [(TTF)(2)[Fe(CA)(2)(H(2)O)(2)]](n)(4) (H(2)CA = chloranilic acid, phz = phenazine, [Fe(Cp)(2)] = ferrocene, [Fe(Cp*)(2)] = decamethylferrocene, TTF = tetrathiafulvalene) are described. The guest cations are introduced between the ([Fe(CA)(2)(H(2)O)(2)](m-))(l) layers by electrostatic (1-4) and pi-pi stacking (3, 4) interactions. [Fe(Cp*)(2)](+) cations in 3 are stacked on each other making tilted columns which are included in the channel created by the chlorine atoms of CA(2-) dianions. TTF cations in 4 are stacked face to face with two types of S...S distances (type A; 3.579(3) A, and type B; 3.618(3) A) making a columnar structure. The TTF cations in the stacked column have a head-to-tail arrangement with respect to the iron-chloranilate layer. Mössbauer spectroscopy suggests that [Fe(CA)(2)(H(2)O)(2)](m-) anion in 3 is consistent with high-spin (S = 5/2) iron(III) ions and [Fe(Cp*)(2)](+) in the low-spin (S = 1/2) iron(III) ions. In 4, Mössbauer spectroscopy shows high-spin iron(II) ions (IS = 1.10 mm.s(-1) and QS = 1.66 mm.s(-1) at 297 K) and high-spin iron(III) ions (IS = 0.42 mm.s(-1) and QS = 1.27 mm.s(-1) at 297 K), suggesting that the anionic layer of iron-chloranilate has a valence-trapped mixed-valence state. At the temperature range of 77-300 K, the compounds 1, 2, and 3 are EPR silent, whereas the EPR spectrum of 4 shows two types of signals with g = 2.008 indicating the radical form of TTF.
authors.affiliation: Department of Chemistry, Shizuoka University, Ohya, Shizuoka 422-8529, Japan.
authors.forename: Kunimitsu
authors.initials: K
authors.lastname: Nagayoshi
authors.forename: Md Khayrul
authors.initials: MK
authors.lastname: Kabir
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Tobita
authors.forename: Kenji
authors.initials: K
authors.lastname: Honda
authors.forename: Mitsuhiro
authors.initials: M
authors.lastname: Kawahara
authors.forename: Motomi
authors.initials: M
authors.lastname: Katada
authors.forename: Keiichi
authors.initials: K
authors.lastname: Adachi
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Nishikawa
authors.forename: Isao
authors.initials: I
authors.lastname: Ikemoto
authors.forename: Hitoshi
authors.initials: H
authors.lastname: Kumagai
authors.forename: Yuko
authors.initials: Y
authors.lastname: Hosokoshi
authors.forename: Katsuya
authors.initials: K
authors.lastname: Inoue
authors.forename: Susumu
authors.initials: S
authors.lastname: Kitagawa
authors.forename: Satoshi
authors.initials: S
authors.lastname: Kawata