TY - JOUR
T1 - Formation of 2
T2 - 1 insulating complexes of D+· D+· A2- alternating stack and a 4:1 semimetallic complex using M(dto)2 dianions (M = Ni, Pd or Pt and dto = dithiooxalate)
AU - Saito, Gunzi
AU - Izukashi, Hiroko
AU - Shibata, Michihiro
AU - Yoshida, Keisuke
AU - Kushch, Lyudmila A.
AU - Kondo, Tetsuo
AU - Yamochi, Hideki
AU - Drozdova, Olga O.
AU - Matsumoto, Kiyoshi
AU - Kusunoki, Masami
AU - Sakaguchi, Ken ichi
AU - Kojima, Norimichi
AU - Yagubskii, Eduard B.
PY - 2000
Y1 - 2000
N2 - The preparation of charge transfer (CT) complexes of dithiooxalate (dto) transition metal salts M(dto)2 (M =Ni, Pd, Pt or Cu) with a variety of electron donor molecules was examined based on the redox properties of constituent molecules. Conventional electron donors of TTF type, such as bis(ethylenedithio)- (BEDT-TTF (ET)) and bis(ethylenedioxy)- tetrathiafulvalene (BEDO-TTF (BO)), mainly afford 2:1 solid CT complexes composed of a donor cation dimer D+·D+· and dianion of M(dto)2 (A2-) when M =Ni, Pd or Pt. The constituent molecules stack alternately to construct a D+·D+· A2- column. Their crystal structures are unique among the ET and BO complexes so far known, namely the M(dto)22- ions are isolated from each other being surrounded by six dimers of D+· in the crystals. Three kinds of 2:1 complex were obtained between ET and Pd(dto)2. The electronic spectra of the solids are characterized by the particular intradimer transition of the donor cation dimer. The infrared vibrational spectra strongly exhibit the as modes of the donor cation due to its dimerization. All of the complexes are electrical insulators. A singlet- triplet magnetic excitation is clearly observed for some of them. A highly conductive 4:1 complex was obtained between ET and Pd(dto)2, (ET)4[Pd(dto)2], which exhibited electronic absorption extending below 5 x 103 cm-1. The complex shows a semimetallic nature.
AB - The preparation of charge transfer (CT) complexes of dithiooxalate (dto) transition metal salts M(dto)2 (M =Ni, Pd, Pt or Cu) with a variety of electron donor molecules was examined based on the redox properties of constituent molecules. Conventional electron donors of TTF type, such as bis(ethylenedithio)- (BEDT-TTF (ET)) and bis(ethylenedioxy)- tetrathiafulvalene (BEDO-TTF (BO)), mainly afford 2:1 solid CT complexes composed of a donor cation dimer D+·D+· and dianion of M(dto)2 (A2-) when M =Ni, Pd or Pt. The constituent molecules stack alternately to construct a D+·D+· A2- column. Their crystal structures are unique among the ET and BO complexes so far known, namely the M(dto)22- ions are isolated from each other being surrounded by six dimers of D+· in the crystals. Three kinds of 2:1 complex were obtained between ET and Pd(dto)2. The electronic spectra of the solids are characterized by the particular intradimer transition of the donor cation dimer. The infrared vibrational spectra strongly exhibit the as modes of the donor cation due to its dimerization. All of the complexes are electrical insulators. A singlet- triplet magnetic excitation is clearly observed for some of them. A highly conductive 4:1 complex was obtained between ET and Pd(dto)2, (ET)4[Pd(dto)2], which exhibited electronic absorption extending below 5 x 103 cm-1. The complex shows a semimetallic nature.
UR - http://www.scopus.com/inward/record.url?scp=0034077974&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0034077974&partnerID=8YFLogxK
U2 - 10.1039/a908670f
DO - 10.1039/a908670f
M3 - Article
AN - SCOPUS:0034077974
SN - 0959-9428
VL - 10
SP - 893
EP - 910
JO - Journal of Materials Chemistry
JF - Journal of Materials Chemistry
IS - 4
ER -