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Temperature-Dependent FT-IR Spectroscopy Study of Silver 1,9-Nonanedithiolate

Volume 55, Number 8 (Aug. 2001) Page 1085-1091

Choi, Hyouk Jin; Han, Sang Woo; Lee, Seung Joon; Kim, Kwan

The structure and thermal behavior of silver 1,9-nonanedithiolate (AgNDT) is investigated by means of diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and elemental analysis. The XRD data suggests that AgNDT has a layered structure but with poor registry between layers. The poor registry seems to be associated with the deficiency of Ag by 20% in binding to the available sulfur atoms. DRIFT spectral data nonetheless indicates that the carbon chains take nearly all-trans conformation. The temperature-dependent DRIFT spectral data suggests that AgNDT should degrade at >530 K without any thermodynamic phase transition, in agreement with the TGA and DSC analysis. The finding that AgNDT does not exhibit liquid-crystalline behavior upon melting is attributed to the formation of two Ag-S bonds (as α,ω-dithiolate) in AgNDT, even though each Ag atom is trigonally bonded to sulfur, as in silver monothiolate (AgSR).