The unconventional semiconductors represent two novel structure types of polythiometalates: syntheses, structures and electrical properties of {[W3Ag3S12]center dot[La(DMAC)(5)(H2O)(3)center dot(DMAC)(4)]}(n) and {[W8Ag10S32]center dot[M(DEF)(8)](2)}(n) (M = La, Nd)
L. Chen et al., The unconventional semiconductors represent two novel structure types of polythiometalates: syntheses, structures and electrical properties of {[W3Ag3S12]center dot[La(DMAC)(5)(H2O)(3)center dot(DMAC)(4)]}(n) and {[W8Ag10S32]center dot[M(DEF)(8)](2)}(n) (M = La, Nd), J CHEM S DA, (24), 1999, pp. 4303-4307
Citations number
33
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
Polymeric transition metal chalcogenides have attracted much attention beca
use of their possible properties directly derived from their peculiar struc
tures. Compared with polyoxometalates, polythiometalate chemistry is still
very young. We report here the syntheses, structural characterizations and
electrical properties of the novel polythiometalates, {[W3Ag3S12].[La(DMAC)
(5)(H2O)(3).(DMAC)(4)]} 1 and {[W8Ag10S32].[M(DEF)(8)](2)}(n) (M=La 2 and M
=Nd 3). The complexes were obtained by self-assembly of (NH4)WS4 and AgNO3
with Ln(NO3)(3) (Ln=La, Nd) in different solvents: DMAC (DMAC=N N'-dimethyl
acetamide), DEF (DEF=N ,N'-diethylformamide). The title compounds represent
two novel structure types of W/Ag/S polythiometalates, 1: a single-strande
d helix chain; 2 and 3 are isomorphous: equal step zigzag chains with a dou
ble square unit. The unusual 1 has two helices: an anion chain and a cation
chain simultaneously exist in the unit cell and the anion helix is defined
by a pitch (length per turn) of 17.65 Angstrom, and a radius of circumscri
bed cylinder of 8.88 Angstrom. Room temperature conductivities of 1, 2/3 ar
e 1.16x10(-4), 2.58x10(-4) S cm(-1).