Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:36–43, 2011
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2010.522674
Preparation of Tin Chalcogenide Nanoparticles Using
Tribenzyltin(IV) Semi- and Thiosemicarbazone Precursors
Yogesh S. Niwate and Shivram S. Garje
Department of Chemistry, University of Mumbai, Vidyanagari, Mumbai, India
sulfides are used as semiconductors,[13] holographic record-
ing media,[14] and solar collectors as high conversion effi-
ciency photovoltaic materials.[15] Tin oxide has applications in
gas-sensors,[16] catalysis,[17] electrochromic windows,[18] and
photodetectors.[19]
The reactions of tribenzyltin(IV)chloride with one mole equiv-
alent of sodium salts of semi- and thiosemicarbazone ligands gave
complexes of the type Bz3SnL (L = semicarbazone or thiosemi-
carbazone moiety). These compounds have been characterized by
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elemental analysis, IR, 1H, 13C{ H}, and 119Sn (in few cases), NMR
Various methods have been used for the preparation of tin
chalcogenide nanocrystallites. Tin sulfide nanoparticles can
be prepared by dispersing melted tin in a sulfur-dissolved
solvent.[20] Also, precursors such as [Sn(SCH2 – CF3)4] and
[Sn(SPh)4] have been used. However, they may require H2S gas
as a source of sulfur.[21,22] This could be due to disulfide elimina-
tion, which results from non-covalently bonded S S interaction
in the precursor molecules.[23,24] In the present study, we report
preparations of tribenzyltin(IV) semi- and thiosemicarbazone
complexes and their further use as single source precursors.
It is found that semicarbazone derivatives result in tin oxide
(SnO) whereas thiosemicarbazones gave tin sulfide (SnS). The
structures of the ligands used and the probable structures of the
resulting complexes are given Figure 1 and Figure 2, respec-
tively.
spectroscopy, and thermogravimetric analysis. Thermal decom-
position of complexes was carried out. The materials obtained
were characterized by powder X-ray diffraction (XRD), transmis-
sion electron microscopy (TEM), energy dispersive X-ray analy-
sis, absorption, and fluorescence spectroscopy. The XRD showed
formation of SnS and SnO from thiosemicarbazone and semicar-
bazone complexes, respectively. The TEM images showed presence
of nearly spherical particles.
Keywords nanocrystallites, single source precursors, semi- and
thiosemicarbazones, tin oxide, tin sulfide
INTRODUCTION
Recently, much attention is being paid to the ‘nanomate-
rials’ due to their interesting physical and chemical proper-
ties, as well as their applications.[1] This has resulted into
development of newer preparation methods, such as thermal
decomposition,[2] chemical reduction,[3] electrodeposition,[4]
solvothermal route,[5] etc. for the preparation of these mate-
rials. These methods have been utilized for the preparation
of nanocrystallites of metals,[6,7] metal oxides,[8] and metal
sulfides.[9,10] Tin sulfides and oxides are important materials.
Tin forms many binary sulfides such as SnS, SnS2, Sn2S3,
etc.[11] Similarly, tin also forms binary oxides, such as SnO,
SnO2, Sn2O3, etc.[12] SnO has litharge structure, SnO2 has
rutile structure, whereas Sn2O3 exists in a layered structure.
Tin chalcogenides have many applications. For example, tin
EXPERIMENTAL
Materials and Equipments
All the reactions were carried out in the oxygen free nitrogen
atmosphere. The analytical grade solvents were used and they
were dried prior to use. Tribenzyltin(IV)chloride,[25] thiosemi-
carbazones and semicarbazones were prepared by the reported
methods.[26] Tin was determined as SnO2 gravimetrically[27]
and chlorine was determined by Volhard’s method.[27] Elemen-
tal analyses (C, H, N, S) of all the compounds were carried
out on Thermo Finnigan, Italy Model FLASH EA 1112 Series
elemental analyser. Infrared spectra were recorded as KBr pel-
lets in the region 4000–400 cm−1 on Perkin-Elmer Spectrum
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One FTIR spectrometer. 1H, 13C { H} and 119Sn NMR spectra
Received 14 July 2010; accepted 3 August 2010.
were recorded in 5 mm NMR tube in dmso-d6 on a Brucker-300
spectrometer. The chemical shifts are relative to internal stan-
The authors thank TIFR, Mumbai for providing XRD. Thanks are
due to SAIF, IIT Bombay for recording TEM images and elemen-
tal analysis. The financial assistance provided by Narotam Sekhsaria
Foundation is gratefully acknowledged.
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dard tetramethylsilane for 1H and 13C { H} and tetramethyltin
for 119Sn. The electronic spectra were recorded on a UV-2401
PC Shimadzu spectrophotometer. The fluorescence spectra were
recorded on a RF-5301PC Shimadzu spectrofluorophotometer.
Address correspondence to Shivram S. Garje, Department of Chem-
istry, University of Mumbai, Vidyanagari, Santacruz (East), Mumbai –
400 098, India. E-mail: ssgarje@chem.mu.ac.in
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Niwate, Yogesh S.
