Molecular conductors from neutral-radical charge-transfer salts. Preparation and characterization of an iodine-doped hexagonal phase of 1,2,3,5-dithiadiazolyl ([HCN[sub 2]S[sub 2]][sup [lg bullet]])

Journal Article · Wed Feb 23 00:00:00 EST 1994 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00083a005· OSTI ID:7301902

Bryan, C D; Cordes, A W ^[1]; Haddon, R C; Palstra, T T.M.; Perel, A S; Schneemeyer, L F; Waszczak, J V ^[2]; Hicks, R G; Kennepohl, D K; MacKinnon, C D; Oakley, R T; Scott, S R ^[3]

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1. Univ. of Arkansas, Fayetteville, AR (United States)
2. AT T Bell Lab., Murray Hill, NJ (United States)
3. Univ. of Guelph, Ontario (Canada)

Sublimation of 1,2,3,5-dithiadiazolyl in vacuo affords a triclinic phase of the dimer [HCN[sub 2]S[sub 2]][sub 2]. The crystals belong to the space group P[bar 1], a = 6.816(3), b = 13.940(2), c = 14,403(3) [angstrom], [alpha] = 116,830(14), [beta] = 98,64(3), [gamma] = 99,18(3)[degrees], FW = 212.4 (for [HCN[sub 2]S[sub 2]][sub 2][center dot][N[sub 2]][sub 0.08]), Z = 6. The crystal structure consists of stacked dimers, with three dimers per aymmetric unit. Pairs of asymmetric units, related by an inversion center, generate a pinwheel motif consisting of six dimers. The columnar structure associated with these pinwheels forms close-packed sets of [open quotes]molecular tubes[close quotes]. Cosublimation of the radical in the presence of iodine in the mole ratio (HCN[sub 2]S[sub 2]:I = 5:1) yields an iodine-doped hexagonal phase of composition [HCN[sub 2]S[sub 2]][sub 6][I][sub 1.1]. Crystals of this material belong to the space group P6[sub 1], a = b = 14.132(16), c = 3.352(5) [angstrom]. FW = 128.20, Z = 6. The crystal structure consists of sixfold pinwheels in which the now evenly spaced HCN[sub 2]S[sub 2] rings form a spiral about the 6[sub 1] axis. The iodine atoms lie within the columnar cavity of the pinwheels in a disordered array wrapped tightly about the sixfold screw axis. The single-crystal conductivity of the doped material is 15 S cm[sup [minus]1] at room temperature. Raman spectroscopic and magnetic susceptibility measurements on the doped material are reported. 22 refs., 6 figs., 4 tabs.

• OSTI ID: 7301902
• Journal Information: Journal of the American Chemical Society; (United States), Vol. 116:4; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
DOPED MATERIALS
ELECTRIC CONDUCTIVITY
MAGNETIC SUSCEPTIBILITY
THIADIAZOLES
CRYSTAL STRUCTURE
RAMAN SPECTRA
SUBLIMATION
SYNTHESIS
CHARGE TRANSPORT
COMPILED DATA
CRYSTAL DOPING
HEXAGONAL LATTICES
IODINE
MONOCRYSTALS
ORGANIC SEMICONDUCTORS
RADICALS
SALTS
AZOLES
CRYSTAL LATTICES
CRYSTALS
DATA
ELECTRICAL PROPERTIES
ELEMENTS
EVAPORATION
HALOGENS
HETEROCYCLIC COMPOUNDS
INFORMATION
MAGNETIC PROPERTIES
MATERIALS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHASE TRANSFORMATIONS
PHYSICAL PROPERTIES
SEMICONDUCTOR MATERIALS
SPECTRA
400201* - Chemical & Physicochemical Properties
665000 - Physics of Condensed Matter- (1992-)