Chem. Mater.

2001, 13, 2103-2111 2103

Use of Dialkyldithiocarbamato Complexes of

Bismuth(III) for the Preparation of Nano- and
Microsized Bi2S3 Particles and the X-ray Crystal
Structures of [Bi{S2CN(CH3)(C6H13)}3] and
[Bi{S2CN(CH3)(C6H13)}3(C12H8N2)]
Olinda C. Monteiro, Helena I. S. Nogueira, and Tito Trindade*
Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal

Majid Motevalli
Department of Chemistry, Queen Mary & Westfield College, Mile End Road,
London E1 4NS, United Kingdom
Received December 12, 2000. Revised Manuscript Received February 24, 2001

A range of bismuth(III) dithiocarbamato complexes were prepared and characterized. The

X-ray crystal structures of the compounds [Bi{S2CN(CH3)(C6H13)}3] (1) and [Bi{S2CN(CH3)-
(C6H13)}3(C12H8N2)] (2) are reported. The preparation of Bi2S3 particulates using a wet
chemical method and involving the thermalysis of Bi(III) dialkyldithiocarbamato complexes
is described. The influence of several experimental parameters on the optical and
morphological properties of the Bi2S3 powders was investigated. Nanosized Bi2S3 colloids
were obtained having long-term stability and showing a blue shift on the optical band edge;
the presence of particles exhibiting quantum size effects is discussed. Morphological well-
defined Bi2S3 particles were obtained in which the fiber-type morphology is prevalent.

1. Introduction have received less attention.12-14 Macrocrystalline Bi2S3

has been investigated as a material for photodiode
Synthetic methods and physical properties of semi- arrays and photovoltaic devices.15,16 Besides its techno-
conducting nanocrystals (or quantum dots) have been logical interest, it has been suggested that because of
the subject of active research during the past decade.1-5 its anisotropic structure, layers of lamellar semiconduc-
In such materials, the charge carriers are confined tors may be regarded as colloidal analogues of quantum
within what is effectively a small portion of the bulk well structures.17,18 Therefore, quantum confinement of
crystalline lattice. In this size regime, quantum confine- the charge carriers would occur, provided at least one
ment effects are observed and the band gap of the dimension of the particles is located within the nanosize
semiconductor widens as the particle size decreases to regime. Studies reporting such behavior for Bi2S3 have
dimensions comparable to the exciton Bohr radius.1 been scarce because of the lack of theoretical data and
Band gap tuning in nanophase semiconductors, among also of reliable synthetic methods that give Bi2S3
other properties such as the capability for surface particulates with well-defined morphologies.
derivatization, has been a possibility by using a plethora
of chemical methods.1-5 Most of such synthetic methods We have been interested in the preparation of nano-
have focused on II/VI semiconductors and on III/V crystalline semiconductors using single-molecule pre-
semiconductors.1-11 Semiconductors having more com- cursors,6,10,19 that is, molecular compounds containing
plex structures, such as bismuth sulfide (Bi2S3, bis-
muthinite), which crystallizes in a lamellar structure, (11) Guzelian, A.; Katari, J.; Kadavanich, A.; Banin, U.; Hanad,
K.; Juban, E.; Alvisatos, A. P.; Wolters, R.; Arnold, C.; Heath, J. J.
Phys. Chem. 1996, 100, 7212.
* To whom correspondence should be addressed. E-mail: ttrindade@ (12) Variano, B. F.; Hwang, D. M.; Sandroff, C. J.; Wiltzius, P.; Jing,
dq.ua.pt. Fax: + 351 234 370 084. T. W.; Ong, N. P. J. Phys. Chem. 1987, 91, 6455.
(1) Steigerwald, M. L.; Brus, L. E. Acc. Chem. Res. 1990, 23, 183. (13) Lifshitz, E.; Yassen, M.; Bykov, L.; Dag, I.; Chaim, R. J. Phys.
(2) Fendler, J. H.; Meldrum, F. C. Adv. Mater. 1995, 7, 607. Chem. 1994, 98, 1459.
(3) Alvisatos, A. P. J. Phys. Chem. 1996, 100, 13226. (14) Mu, R.; Tung, Y. S.; Ueda, A.; Henderson, D. O. J. Phys. Chem.
(4) Weller, H. Adv. Mater. 1993, 5, 88. 1996, 100, 19927.
(5) Hagfeldt, A.; Grätzel, M. Chem. Rev. 1995, 95, 49. (15) Pawar, S. H.; Bhosale, P. N.; Uplane, M. D.; Tamhankar, S.
(6) Trindade, T.; O’Brien, P.; Zhang, X. Chem. Mater. 1997, 9, 523. Thin Solid Films 1983, 110, 165.
(7) Trindade, T.; O’Brien, P. Adv. Mater. 1996, 8, 161. (16) Killedar, V. V.; Lokhande, C. D.; Bhosale, C. H. Thin Solid
(8) Khan-Lodhi, A.; Robison, B. H.; Towey, T.; Herramann, C.; Films 1996, 289, 14.
Knoche, W.; Thesing, U. In Structure, Dynamics and Equilibrium (17) Sandroff, C. J.; Hwang, D. M.; Chung, W. M. Phys. Rev. B 1986,
Properties of Colloid Systems; Kluwer: Dordrecht, 1990; p 373. 33, 5953.
(9) Murry, C. B.; Norris, D. J.; Bawendi, M. G. J. Am. Chem. Soc. (18) Sandroff, C. J.; Kelty, S. P.; Hwang, D. M. J. Chem. Phys. 1986,
1993, 115, 8706. 85, 5337.
(10) Trindade, T.; O’Brien, P.; Zhang, X.; Motevalli, M. J. Mater. (19) Trindade, T.; Monteiro, O. C.; O’Brien, P.; Motevalli, M.
Chem. 1997, 7, 1011. Polyhedron 1999, 18, 1171.

10.1021/cm000973y CCC: $20.00 © 2001 American Chemical Society

Published on Web 05/11/2001
2104 Chem. Mater., Vol. 13, No. 6, 2001 Monteiro et al.

both elements of the semiconductor within a single [Bi(S2CNMenHex)3]. 1H NMR: δ 0.89 [3H, t, (CH2)5CH3];
molecule, for example, metal dithiocarbamato com- δ 1.31 [6H, t, (CH2)2(CH2)3CH3]; δ 1.74 [2H, m, CH2CH2(CH2)3-
plexes. The use of tris(benzylthiolato)bismuth to CH3]; δ 3.36 [3H, s, CH3]; δ 3.78 [2H, t, CH2(CH2)4CH3]. 13C
NMR: δ 13.96 [(CH2)5CH3]; δ 22.51[(CH2)4CH2CH3]; δ 26.43
produce pure polycrystalline Bi2S3 is reported in the [(CH2)3CH2CH2CH3]; δ 26.79 [(CH2)2CH2(CH2)2CH3]; δ 31.40
literature.20 Recently, we showed that the compound [CH2CH2(CH2)3CH3]; δ 41.80 [CH3]; δ 56.67 [CH2(CH2)4CH3];
bismuth(III) methyl-n-hexyl-dithiocarbamate ([Bi{S2- δ 201.41 [S2CN]. Elemental analysis (%). Found: C, 35.66; H,
CN(CH3)(C6H13)}3]) is a useful single-molecule precursor 5.51; N, 5.20; S, 24.45. Calcd: C, 36.97; H, 6.16; N, 5.39; S,
to produce fiber-type Bi2S3 particles, either in organic 24.65. IR major bands (ν/cm-1): 1491 [ν(C-N)], 957 [ν(C-S)].
solution21 or by a CVD method.22 Here, we report a more Yield 70%. mp 105 °C.
[Bi(S2CNMenBu)3]. 1H NMR: δ 0.94 [3H, t, (CH2)3CH3]; δ
detailed study using other single-molecule precursors
1.35 [2H, m, (CH2)2CH2CH3]; δ 1.73 [2H, m, CH2CH2CH2CH3];
to prepare nano- and microcrystalline Bi2S3 powders by δ 3.36 [3H, s, CH3]; δ 3.79 [2H, t, CH2(CH2)2CH3]. 13C NMR:
thermalysis in high boiling point solvents. The influence δ 13.74 [(CH2)3CH3]; δ 20.02 [(CH2)2CH2CH3]; δ 28.87 [CH2-
of several synthetic parameters on the final morphologi- CH2CH2CH3]; δ 56.44 [CH2(CH2)2CH3]; δ 201.42 [S2CN].
cal and optical properties of the powders is reported. Elemental analysis (%). Found: C, 30.21; H, 4.76; N, 5.91; S,
Moreover, our interest in the production of Bi2S3 29.50. Calcd: C, 31.08; H, 5.18; N, 6.04; S, 27.63. IR major
materials using such compounds led us to investigate bands (ν/cm-1): 1488 [ν(C-N)], 953 [ν(C-S)]. Yield 91%. mp
143 °C.
some structural features inherent to bismuth(III) dithio- [Bi(S2CNEt2)3]. 1H NMR: δ 1.33 [6H, t, CH2CH3]; δ 3.83
carbamato complexes, in particular, the asymmetric [4H, q, CH2CH3]. 13C NMR: δ 12.21 [CH2CH3]; δ 48.30 [CH2-
alkyl derivatives. Bismuth(III) dithiocarbamato com- CH3]; δ 200.46 [S2CN]. Elemental analysis (%). Found: C,
plexes have been known for a long time and crystal 26.82; H, 4.13; N, 6.29; S, 31.65. Calcd: C, 27.56; H, 4.59; N,
structures have been reported for [Bi(S2CNEt2)3]23 and 6.43; S, 29.40. IR major bands (ν/cm-1): 1490 [ν(C-N)], 983
a number of [Bi(S2CNEt2)3] halogen substituted com- [ν(C-S)]. Yield 45%. mp 201 °C.
[Bi(S2CNnBu2)3]. 1H NMR: δ 0.94 [3H, t, (CH2)3CH3]; δ 1.34
plexes.24-28 Here are reported for the first time X-ray [2H, m, (CH2)2CH2CH3]; δ 1.75 [2H, m, CH2CH2CH2CH3]; δ
crystal structures of asymmetric bismuth(III) N,N- 3.73 [2H, t, CH2(CH2)2CH3]. 13C NMR, δ 13.71 [(CH2)3CH3];
dialkyl dithiocarbamato complexes, namely, for the 20.11[(CH2)2CH2CH3]; δ 28.92 [CH2CH2CH2CH3]; δ 53.94
compounds [Bi{S2CN(CH3)(C6H13)}3] (1) and [Bi{S2CN- [CH2(CH2)2CH3]; δ 200.90 [S2CN]. Elemental analysis (%).
(CH3)(C6H13)}3(C12H8N2)] (2). Found: C, 38.29; H, 5.91; N, 4.95; S, 24.44. Calcd: C, 39.46;
H, 6.58; N, 5.12; S, 23.39. IR major bands (ν/cm-1): 1483 [ν-
(C-N)], 956 [ν(C-S)]. Yield 56%. mp 99 °C.
2. Experimental Section [Bi(S2CNMenHex)3(C12H8N2)]. 1H NMR: δ 0.88 [3H, t,
All chemicals were supplied by Aldrich except Bi2O3 and dry (CH2)5CH3]; δ 1.30 [6H, t, (CH2)2(CH2)3CH3]; δ 1.73 [2H, m,
methanol (Merck), and toluene and 2-ethoxyethanol (Riedel CH2CH2(CH2)3CH3]; δ 3.35 [3H, s, CH3]; δ 3.78 [2H, t,
& Haan). All chemicals were used as received. CH2(CH2)4CH3]. The following peaks are due to the o-phenan-
2.1. Synthesis of Bismuth(III) Dialkyldithiocarbamato throline ligand: δ 7.62 [ H, q]; δ 7.77 [ H, s]; δ 8.23 [ H, t]; δ
Complexes. The complexes [Bi(S2CNMenHex)3], [Bi(S2CNMen- 9.19 [ H, t]. 13C NMR: δ 13.98 [(CH2)5CH3]; δ 22.52 [(CH2)4-
Bu)3], [Bi(S2CNEt2)3], and [Bi(S2CNnBu2)3], in which Me ) CH2CH3]; δ 26.42 [(CH2)3CH2CH2CH3]; δ 26.83 [(CH2)2-
methyl, Et ) ethyl, nBu ) n-butyl, and nHex ) n-hexyl, were CH2(CH2)2CH3]; δ 31.42 [CH2CH2(CH2)3CH3]; δ 41.74 [CH3];
prepared by adaptation of the literature method.29 The syn- δ 56.59 [CH2(CH2)4CH3]; δ 201.48 [S2CN]. The following peaks
thetic method consists of the insertion of CS2 into the second- are due to the o-phenathroline ligand: δ 123.04; δ 126.49; δ
ary amine in the presence of Bi2O3. In a typical synthesis, 128.60; δ 135.97; δ 146.17; δ 150.41. IR bands (ν/cm-1) (major
[Bi(S2CNMenHex)3] was obtained by adding dropwise N- bands): 1486 [ν(C-N)], 974 [ν(C-S)]. Yield 56%. mp 144 °C.
methylhexylamine, 98% (40 mmol), and then CS2 (40 mmol) 2.2. Preparation of Bi2S3 Particulates. Bi2S3 particulates
to a methanol suspension of Bi2O3 (6 mmol; 20 mL). The were prepared by solution thermalysis of the bismuth(III)
mixture continued to react with stirring, at room temperature, dithiocarbamate complexes. The decomposition of such com-
over 24 h. The yellow solid formed was collected by filtration pounds was performed in the solvents p-xylene, 4-ethylpyri-
and the product recrystallized from a hot chloroform:methanol dine, 2-ethoxyethanol, ethyleneglycol (1,2-dihydroxyethane),
mixture (3:1). All bismuth(III) complexes were prepared and tri-n-octylphosphine oxide, which were flushed with N2
similarly using the respective secondary amine. The compound prior to use. All the reactions were performed under a N2
[Bi(S2CNMenHex)3(C12H8N2)] was obtained by stirring an stream, using a round flask heated by an oil bath at the
acetone solution (50 mL) containing [Bi(S2CNMenHex)3] (0.40 required temperature and equipped with a Liebig condenser.
g) and o-phenanthroline: C12H8N2 (0.2 g) over 2 h; the pale The experimental apparatus was placed inside a fume cup-
yellow solid formed was recrystallized from hot acetone. All board equipped with local exhaust ventilation. For each solvent
compounds were characterized by NMR and IR spectroscopies the thermalysis was performed as follows:
and microanalysis. Tri-n-octylphosphine oxide (TOPO). [Bi(S2CNRR′)3] (0.2
mmol) was dissolved in 10 mL of tri-n-octylphosphine (TOP).
This solution was carefully injected into 25 g of TOPO, while
(20) Boudjouk, P.; Remington, M. P., Jr.; Grier, D. G.; Jarabek, B. stirring, at 150 °C over 2 h. The mixture was then cooled to
R.; McCarthy, G. J. Inorg. Chem. 1998, 37, 3538.
(21) Monteiro, O. C.; Trindade, T. J. Mater. Sci. Lett. 2000, 19, 859. 60 °C and an excess of methanol was added. The powder
(22) Monteiro, O. C.; Trindade, T.; Park, J.-H.; O’Brien, P. Chem. obtained was isolated by centrifugation and washed with
Vap. Dep. 2000, 6, 230. methanol.
(23) Raston, C. L.; White, A. H. J. Chem. Soc., Dalton 1976, 791. 2-Ethoxyethanol. A solution of the precursor (0.20 mmol) in
(24) Raston, C. L.; Rowbottom, G. L.; White, A. H. J. Chem. Soc., 2-ethoxyethanol (50 mL) was refluxed (132 °C) over 2 h. The
Dalton 1981, 1352.
(25) Raston, C. L.; Rowbottom, G. L.; White, A. H. J. Chem. Soc.,
solution was then left to cool to room temperature The solid
Dalton 1981, 1366. formed was isolated by centrifugation and washed with
(26) Raston, C. L.; Rowbottom, G. L.; White, A. H. J. Chem. Soc., n-hexane. The dark powder obtained was dispersed in organic
Dalton 1981, 1369. solvents such as dichlorometane, pyridine, and acetone.
(27) Raston, C. L.; Rowbottom, G. L.; White, A. H. J. Chem. Soc., Ethyleneglycol, 4-Ethylpyridine, and p-Xylene. The ther-
Dalton 1981, 1379. malysis of the bismuth complexes using these solvents was
(28) Raston, C. L.; Rowbottom, G. L.; White, A. H. J. Chem. Soc.,
Dalton 1981, 1383. performed at the solvent reflux temperature, using a procedure
(29) Nomura, R.; Kanaya, K.; Matsuda, H. Bull. Chem. Soc. Jpn. similar to the one used with 2-ethoxyethanol. The powders
1989, 62, 939. obtained in the presence of ethyleneglycol were washed with
Dialkyldithiocarbamato Complexes of Bismuth(III) Chem. Mater., Vol. 13, No. 6, 2001 2105

Table 1. Crystal Data and Structure Refinement of [Bi(S2CNMenHex)3] and [Bi(S2CNMenHex)3(C12H8N2)]

empirical formula C24H48BiN3S6 C36H56BiN5S6
formula weight 779.99 960.20
temperature 293(2) K 180(2) K
wavelength 0.71073 Å 0.71073 Å
crystal system monoclinic triclinic
space group P21/c P1
unit cell dimensions a ) 19.833(3) Å, R ) 90° a ) 10.401(8) Å, R ) 105.36(5)°
b ) 17.423(3) Å, â ) 104.57(2)° b ) 14.598(9) Å, â ) 80.64(6)°
c ) 10.145(2) Å, γ ) 90° c ) 15.341(9) Å, γ ) 108.19(5)°
volume 3392.9(10) Å3 2126(2) Å3
Z 4 2
density (calculated) 1.527 Mg/m3 1.500 Mg/m3
absorption coefficient 5.583 mm-1 4.473 mm-1
F(000) 1568 972
crystal size 0.2 × 0.2 × 0.1 mm3 0.4 × 0.3 × 0.2 mm3
θ range for data collection 1.58°-24.98° 1.51°-25.10°
index ranges 0 e h e 23, 0 e k e 20 -1 e h e 12, -17 e k e 16
-12 e l e 11 -17 e l e 18
reflections collected 6119 8198
independent reflections 5940 [R(int) ) 0.0527] 7500 [R(int) ) 0.0372]
completeness to θ ) 24.98° 99.8% 98.8%
refinement method full-matrix least-squares on F2 full-matrix least-squares on F2
data/ restrains/parameters 5940/90/313 7500/9/439
goodness-of-fit on F2 1.007 1.001
final R indices [I > 2σ(I)] R1 ) 0.0591, wR2 ) 0.1720 R1 ) 0.0395, wR2 ) 0.1015
R indices (all data) R1 ) 0.1414, wR2 ) 0.2364 R1 ) 0.0518, wR2 ) 0.1053
largest diff peak and hole 2.668 and -2.754 e‚Å-3 1.306 and -1.259 e‚Å-3

methanol and then dispersed in solvents such as dichloro-

methane or pyridine. When 4-ethylpyridine was used as the
solvent, the powder obtained was washed with n-hexane and
dispersed in dichloromethane. The decomposition of the bis-
muth complexes in p-xylene resulted in the formation of a
powder that did not disperse in organic solvents.
2.3. Instruments and Characterization. Crystallogra-
phy. The intensity data were collected on an Enraf Nonius
CAD-4 diffractometer using Mo KR radiation (λ ) 0.71069 Å)
with an ω-2θ scan at 180 K. The unit cell parameters were
determined by least-squares refinement on diffractometer
angles 9.38° e θ e 12.15° (1) and 8.411° e θ e 12.72° (2) for
25 automatically centered reflections in each case.30 Crystal
data are summarized in Table 1. All data were corrected for
absorption by semiempirical methods (ψ scan)31 and for
Lorentz-polarization effects by XCAD4.32 The structure was
solved by the Patterson method using SHELXS-9733 and
refined anisotropically (non-hydrogen atoms) by full-matrix
least-squares on F2 using the SHELXL-97 program.33 The H
atoms were calculated geometrically and refined with a riding
model. The program ORTEP-334 was used for drawing the
molecules. WINGX35 was used to prepare material for publica-
tion.
Spectroscopic Methods. The UV/visible absorption spectra
were recorded on a Jasco V-560 UV/VIS spectrophotometer,
using quartz cuvettes and the respective solvent as reference. Figure 1. Molecular structure of [Bi(S2CNMenHex)3].
The NMR spectra were recorded on a Bruker AMX 300
spectrometer using CDCl3 + TMS solutions. The infrared Transmission electron microscopy (TEM) was carried out
spectra were recorded on a Matson 700 FTIR Spectrometer on a Hitachi H-9000 microscope operating at 300 kV. An
using dry KBr disks. aliquot containing the nanodispersed sample was placed on a
Powder Diffraction and Microscopy Techniques. X-ray pow- copper grid coated with an amorphous carbon film and then
der diffraction (XRD) was performed on powders deposited on the solvent was evaporated.
silicon substrates, using a Philips X’Pert instrument operating Scanning electron microscopy (SEM) images and energy-
with Cu KR radiation (λ ) 1.54178 Å) at 40 kV/50 mA. dispersive X-ray (EDAX) measurements results were obtained
using a FEG-SEM Hitachi S4100 microscope operating at 25
kV. The samples were prepared by deposition of an aliquot of
(30) Enraf-Nonius CAD-4/PC Software, Version 1.5c; Enraf-Non-
ius: Delft, The Netherlands, 1992.
the sample on aluminum pieces.
(31) North, A. C. T.; Phillips, D. C.; Mathews, F. S. Acta Crystal-
loger., Sect. A 1968, 42, 351-359. 3. Results and Discussion
(32) Harms, K. XCAD4. Program for data reduction; Philipps-
Universität, Marburg, Germany, 1996.
(33) Sheldrick, G. M. SHELX-97 Program for solution and refine-
3.1. Crystal Structures. The molecular structure of
ment of crystal structures; University Gottingen: Germany, 1997. [Bi(S2CNMenHex)3] (1) is shown in Figure 1. The
(34) Farrugia, L. J. ORTEP-3 for Windows. J. Appl. Cryst. 1997, complex comprises a bismuth atom coordinated by three
30, 565.
(35) Farrugia, L. J., WinGXsA Windows Program for Crystal bidentate asymmetric methyl-n-hexyl dithiocarbamato
Structure Analysis; University of Glasgow: Glasgow, 1998. ligands. Selected bond lengths and angles for this
2106 Chem. Mater., Vol. 13, No. 6, 2001 Monteiro et al.

Table 2. Selected Bond Lengths (Å) and Angles (deg) for results in a distorted coordination environment around
[Bi(S2CNMenHex)3] and [Bi(S2CNMenHex)3(C12H8N2)] the metal center, which is best described as a distorted
1 triangular antiprism. The distortion on the coordination
Bi(1)-S(3) 2.741(2) Bi(1)-S(2) 2.868(2) polyhedron by elongation of the BisS bonds of one of
Bi(1)-S(1) 2.694(3) Bi(1)-S(6) 2.882(3)
the triangular faces of the triangular antiprism may
Bi(1)-S(5) 2.679(2) Bi(1)-S(4) 2.889(2)
result from the presence of a stereochemically active
S(5)-Bi(1)-S(1) 87.27(8) S(1)-Bi(1)-S(6) 95.88(8) electron lone pair along the pseudo-3-fold axis and
S(5)-Bi(1)-S(3) 81.94(7) S(3)-Bi(1)-S(6) 146.17(7) directed to the larger triangular face. The presence of
S(1)-Bi(1)-S(3) 86.01(7) S(2)-Bi(1)-S(6) 117.82(7) the stereochemically active electron lone pair is also
S(5)-Bi(1)-S(2) 152.12(7) S(5)-Bi(1)-S(4) 94.69(7)
S(1)-Bi(1)-S(2) 64.92(7) S(1)-Bi(1)-S(4) 148.75(7) suggested by the bigger angles SsBisS involving the
S(3)-Bi(1)-S(2) 93.63(7) S(3)-Bi(1)-S(4) 63.52(7) three BisS longer bonds (107.99°-117.82°), when com-
S(5)-Bi(1)-S(6) 64.48(7) S(2)-Bi(1)-S(4) 107.99(7) pared to the SsBisS angles involving the three BisS
S(6)-Bi(1)-S(4) 113.12(7) short bonds (81.94°-87.27°). It must be emphasized
2 that, in such a case, the electronic repulsion effects of
Bi(1)-S(3) 2.700(3) Bi(1)-N(5) 2.836(5) the electron lone pair on the coordination geometry of
Bi(1)-N(4) 2.776(5) Bi(1)-S(2) 2.848(2)
Bi(1)-S(1) 2.779(2) Bi(1)-S(6) 2.900(2)
the metal center are less pronounced than those de-
Bi(1)-S(5) 2.794(2) Bi(1)-S(4) 2.966(3) scribed for [Bi(S2CNEt2)3]23 and for [As(S2CNEt2)3].37 A
comparison of the molecular structures of [Bi(S2-
S(3)-Bi(1)-N(4) 160.07(11) N(5)-Bi(1)-S(2) 77.06(11) CNEt)3]23 and [Bi(S2CNMeHex)3] is elucidative with
S(3)-Bi(1)-S(1) 82.29(7) S(3)-Bi(1)-S(6) 100.45(7) respect to the observation of different coordination
N(4)-Bi(1)-S(1) 83.41(12) N(4)-Bi(1)-S(6) 81.66(12)
S(3)-Bi(1)-S(5) 84.12(8) S(1)-Bi(1)-S(6) 139.28(6) geometries for the bismuth by introducing subtle dif-
N(4)-Bi(1)-S(5) 79.24(12) S(5)-Bi(1)-S(6) 62.84(6) ferences in the ligands as it is the case of replacing the
S(1)-Bi(1)-S(5) 77.25(7) N(5)-Bi(1)-S(6) 81.78(11) ethyl groups by an asymmetric set formed by short-
S(3)-Bi(1)-N(5) 141.50(11) S(2)-Bi(1)-S(6) 155.52(5) chain (methyl) and long-chain (n-hexyl) alkyl groups.
N(4)-Bi(1)-N(5) 58.38(15) S(3)-Bi(1)-S(4) 62.90(7)
S(1)-Bi(1)-N(5) 120.79(11) N(4)-Bi(1)-S(4) 136.77(11)
In the compound [Bi(S2CNEt2)3],23 the bismuth coordi-
S(5)-Bi(1)-N(5) 128.39(11) S(1)-Bi(1)-S(4) 130.52(6) nation sphere is completed by the close proximity of a
S(3)-Bi(1)-S(2) 88.80(8) S(5)-Bi(1)-S(4) 128.01(7) S atom from a neighboring molecule at a distance (3.210
N(4)-Bi(1)-S(2) 97.32(12) N(5)-Bi(1)-S(4) 79.36(12) Å) less than the sum of the van der Waals radii.38 The
S(1)-Bi(1)-S(2) 64.06(7) S(2)-Bi(1)-S(4) 80.31(8)
bismuth stereochemistry has been described for such
S(5)-Bi(1)-S(2) 141.26(6) S(6)-Bi(1)-S(4) 83.85(8)
compounds as a distorted dodecahedron by taking in
Table 3. Comparative Bond Distances for Group 15 Metal account the presence of an active electron lone pair.23
Dithiocarbamato Complexes: M-SA and M-SB Refer to It is apparent from Figure 1 that a distinct stereochem-
the Shorter and Longer Distances, Respectively istry is present for bismuth in compound 1. Unlike the
∆ ((M-SB) - complex [Bi(S2CNEt2)3], compound 1 consists of discrete
compound M-SA/Å M-SB/Å (M-SA))/Å units in which intermolecular contacts, comprising the
[As(S2CNEt2)3]a 2.350 2.904 0.554 metal center, within adjacent molecules are not present.
2.344 2.819 0.475 This can be associated with the lengthening of a
2.354 2.812 0.458
[Sb(S2CNEt2)3]b 2.631 2.886 0.255
substituent alkyl group from a two-carbon chain to a
2.487 2.965 0.478 six-carbon chain, resulting in a distinct molecular
2.626 2.895 0.269 packing to accommodate the longer hexyl chain. The
[Bi(S2CNEt2)3]b 2.595 2.956 0.361 nonexistence of intermolecular contacts involving the
2.775 2.964 0.189 metal center favors in this case a less distorted coordi-
2.730 2.908 0.178
[Bi(S2CNMeHex)3] 2.679 2.885 0.206 nation geometry.
2.694 2.868 0.174 A few bismuth N,N-diethyldithiocarbamato complexes
2.741 2.889 0.148 containing nitrogen donors in the coordination sphere
[Bi(S2CNMeHex)3(C12H8N2)] 2.700 2.966 0.266 have been reported by Raston et al.27,28 Because of the
2.794 2.900 0.106
2.779 2.848 0.069 Lewis acidic character and large size of bismuth, the
a
expansion of the coordination number of dithiocarba-
Data from ref 36. b Data from ref 23.
mato bismuth complexes in the presence of Lewis bases
compound are summarized in Table 2. The BisS bonds is favored. However, there are no reports on the
for each dithiocarbamato ligand are asymmetric but structural characterization of such types of complexes
such asymmetry is not so accentuated as in the reported in which the alkyl chains of the dithiocarbamato ligands
structures for diethyldithiocarbamato complexes of Bi, are asymmetric. Figure 2 shows the molecular structure
As, and Sb.23,36,37 Comparative bond distances for metal of the compound [Bi(S2CNMeHex)3(C12H8N2)] (2). Bis-
dithiocarbamato complexes are listed in Table 3. Never- muth is coordinated by three asymmetric bidentate
theless, as described for the complex [As(S2CNEt2)3],37 dithiocarbamato ligands and the coordination sphere is
it is possible to recognize two triangular faces on the expanded in this case by chelation of an o-phenantroline
coordination polyhedron defined by the three BisS short molecule leading to a complex with coordination number
bonds (2.679-2.741 Å) and by the remaining three Bis 8. The BisS distances are within the typical values
S longer bonds (2.868-2.889 Å), both perpendicular to found for this type of compound. The BisN interactions
a pseudorotation 3-fold axis. Such an arrangement are inferior to the sum of the van der Waals radii (<4
Å) and within the range found for BisN distances in
(36) Raston, C. L.; White, A. H. J. Chem. Soc., Dalton 1975, 2425.
(37) Colapietro, M.; Domenicano, A.; Scaramuzza, L.; Vaciago, A. (38) Silvestru, C.; Breunig, H. J.; Althaus, H. Chem. Rev. 1999, 99,
Chem. Commun. 1968, 302. 3277.
Dialkyldithiocarbamato Complexes of Bismuth(III) Chem. Mater., Vol. 13, No. 6, 2001 2107

Table 4. Relevant Experimental Data for the 2-h Thermalysis of [Bi(S2CNMenHex)3] in High Boiling Point Solvents
solvent tempa/°C solid phaseb observations
2-ethoxyethanol 132 Bi2S3 brown powder which disperses easily in hydrocarbons such as CH2Cl2
(leading to long-term stable dispersions)
ethylene glycol 197 Bi2S3 brown powder which disperses easily in hydrocarbons such as CH2Cl2
(leading to long-term stable dispersions)
4-ethylpyridine 168 Bi2S3 brown powder which disperses in hydrocarbons
p-xylene 140 Bi2S3 brown powder which does not disperse in organic solvents
TOPO/TOP 150 Bi2S3 and Bi gray powder which disperses in hydrocarbons
(leading to short-term stable dispersions)
a Reflux except for TOPO/TOP. b As determined by XRD data.

donor atoms. The distortion on the coordination geom-

etry could also be due to the presence of an electron lone-
pair stereochemically active on bismuth. The influence
of the electron lone pair on the coordination geometry
of bismuth is not so evident as that in the previous
compound, 1, which can be related to the expansion of
the coordination number by introducing a bidentate
ligand with a higher bite angle such as o-phenanthro-
line.38 In this case, the distortion from a regular
geometry is possibly due mainly to stereochemical
restrictions imposed by both types of bidentate ligands
with distinct bite angles.
3.2. Preparation of Bi2S3 Nanocrystals. The mo-
lecular precursors 1 and 2 and the complexes [Bi(S2-
CNMenBu)3], [Bi(S2CNEt2)3], and [Bi(S2CNnBu2)3] ther-
mally decompose into pure Bi2S3 under a N2 stream.
This led us to investigate in detail the use of such
compounds as single-molecule precursors to prepare
Bi2S3 particulates. In a preliminary report we have
described the preparation of Bi2S3 nanofibers in 2-ethoxy-
Figure 2. Molecular structure of [Bi(S2CNMenHex)3(C12H8N2)].
ethanol using [Bi(S2CNMenHex)3] as a single-molecule
precursor.21 Here, a more detailed study of the solution
similar compounds.27,28 In complex 2, the BisN inter-
phase thermalysis of bismuth(III) dithiocarbamato com-
actions can be considered as secondary bonds because
plexes is reported. Moreover, the preliminary results21
they are longer than typical BisN covalent bond
suggested that the solvent used had a strong influence
distances, but shorter than the sum of the van der
on the final properties of the Bi2S3 powders. In this
Waals radii.38 The BisS distances are in the range
work, the solution thermalysis of bismuth complexes
2.700-2.966 Å and are close to the sum of the covalent
was investigated using other solvents with higher
radii of the elements (2.54 Å); therefore, the BisS
boiling points and also thermally more stable than
interactions are considered primary bonds. This is
2-ethoxyethanol.39
consistent with the trans influence observed for a
The results obtained from the solution thermal treat-
number of bismuth complexes showing secondary and
ment of the complex [Bi(S2CNMenHex)3] in several
primary BisE bonds, in which E is a nonmetal atom.38
solvents are summarized in Table 4. The treatment of
In fact, for compound 2, in the set of bonds defined by
[Bi(S2CNMenHex)3] in p-xylene led to Bi2S3 powders
the Bi, N(4), N(5), S(3), and S(4) atoms (Figure 2), the
that were not dispersible in any of the organic solvents
shortest secondary bond, that is, the BisN4 bond, is
tested. This result suggested that the particles in this
opposite the longer primary bond, that is, the BisS4
case were not nanosized, a result confirmed later by
bond.
SEM. A possible explanation for this fact is that the
When compared to compound 1, sterical hindrance Bi2S3 primary particles formed during the thermalysis
due to the presence of an additional o-phenanthroline of the precursor do not have a capped surface because
molecule in complex 2 forces the donor atoms to define p-xylene is not a coordinating solvent. Absence of
nearly two planes containing the bismuth atom, which protective agents at the surface of the Bi2S3 nanopar-
are almost orthogonal in relation to each other. The ticles formed facilitates the growth into larger particles
presence of the o-phenantroline molecule in a relative at the high temperature used.
trans position to a dithiocarbamato ligand induces an The thermalysis of [Bi(S2CNMenHex)3] and [Bi(S2-
increase in the asymmetry of the bismuth dithiocarba- CNMenHex)3(C12H8N2)] in TOPO led to a mixture of
mato bond distances. In fact, the higher difference in Bi2S3 and elemental bismuth. The latter was detected
the BisS distances is observed for the dithiocarbamato in the powder as a secondary phase from XRD analysis.
ligand trans to the phenantroline molecule in relation The other solvents tried (2-ethoxyethanol, 4-ethylpyri-
to the plane defined by the remaining S donor ligands. dine, and ethyleneglycol) led to pure Bi2S3, which
Also, in compound 2, the coordination number of bis- disperses in hydrocarbons. The amount of nanomaterial
muth has increased to 8 in relation to the parent
compound 1 and the stereochemistry is best described (39) Vincoli, J. W. Risk Management for Hazardous Chemicals; CRC
as a distorted dodecahedron defined by the S and N Press Lewis Publishers: Boca Raton, FL, 1997; Vol. 2, p 1309.
2108 Chem. Mater., Vol. 13, No. 6, 2001 Monteiro et al.

Figure 3. Optical absorption spectra of Bi2S3 nanodispersed in CH2Cl2, prepared at 132 °C in (a) 4-ethylpyridine, (b)
2-ethoxyethanol, and (c) ethyleneglycol.

Figure 5. TEM image of Bi2S3 nanofibers prepared from [Bi-

(S2CNMenHex)3(C12H8N2)] in ethyleneglycol at 197 °C over 2
h (bar ) 140 nm).
Figure 4. TEM image of Bi2S3 nanofibers prepared from [Bi-
(S2CNMenHex)3] in 2-ethoxyethanol at 132 °C over 2 h (bar ) No meaningful distinct features were observed in the
15 nm). optical spectra of Bi2S3 prepared using distinct bismuth-
prepared in 2-ethoxyethanol was higher than those with (III) dithiocarbamato complexes. This result suggests
other solvents. At room temperature, the molecular that the nature of the alkyl chain of the precursors
precursor [Bi(S2CNMenHex)3] also decomposes in a reported here does not have a strong influence on the
2-ethoxyethanol solution. However, the powders pre- optical properties of the Bi2S3 that results from the
pared in such conditions showed a low crystallinity thermalysis. A red shift on the optical absorption onset
degree and were obtained by stirring the solution over was clearly observed with the increase of the temper-
several days. ature of thermalysis, in agreement with an increase in
The optical spectra of the nanoparticulates prepared the mean particle size, and suggesting a growth process
using 4-ethylpyridine, ethyleneglycol, and 2-ethoxyetha- driven by the reduction of the total surface energy of
nol (at 132 °C for all solvents) are shown in Figure 3. the particulates (Ostwald ripening).
The subtle differences observed on the band profiles of 3.3. Structural and Morphological Characteriza-
the optical spectra (Figure 3) can be associated with tion of Bi2S3 Powders. X-ray powder diffraction
different particle size distributions for the Bi2S3 par- performed on the powders obtained in this work showed
ticles, depending on the solvent used in their prepara- that bismuthinite was the crystalline phase present in
tion. The optical band edge of Bi2S3 for all the samples all the samples, except for those prepared in TOPO in
is considerably shifted to high energy (ca. 0.6 eV) from which elemental bismuth was also detected. The IR
the typical direct band gap of 1.3 eV (952 nm). As will spectra of the powders did not show organic vestiges
be discussed later, this shift may be explained by the either from the solvent or from the molecular precursor.
presence of Bi2S3 nanocrystals in which at least one EDAX measurements performed on the powders showed
linear dimension of the crystallites is nanosized.18 peaks for Bi and S.
Dialkyldithiocarbamato Complexes of Bismuth(III) Chem. Mater., Vol. 13, No. 6, 2001 2109

Figure 6. SEM images of submicrometric Bi2S3 particles prepared in (a) p-xylene (bar ) 0.5 µm), (b) 2-ethoxyethanol (bar ) 1
µm), (c) 4-ethylpyridine (bar ) 0.5 µm), and (d) TOPO/TOP (bar ) 0.5 µm).

To establish the morphological properties of the Bi2S3 plied.12 Compared to nanocrystals of other semiconduc-
nanoparticulates, TEM was performed on samples col- tors (e.g., II/VI materials) in which quantum confine-
lected from a CH2Cl2 solution containing Bi2S3, which ment occurs in a three-dimension box,42 the charge
were deposited on carbon-coated copper grids. Figure 4 carriers in anisotropic lamellar nanostructures are
shows that the Bi2S3 powders prepared in 2-ethoxy- confined in a quantum structure defined by two (disk-
ethanol are composed of nanoparticles with a fiberlike type) or one (fiber-type) linear dimensions.12,18
morphology and with an average linear cross-section Although the fiber-type morphology predominates for
dimension of ca. 6 nm. The low contrast of the TEM Bi2S3 particles prepared using the method reported
images also suggests that the sample consists of very here, it was observed that the particle dimensions were
thin particles of Bi2S3. As reported by others for several strongly dependent on the synthetic parameters used
colloidal layered semiconductors,17,18,40,41 it is reasonable in their preparation, in particular, the type of solvent
to suggest that because of the lamellar-like structure used and the growth temperature. Typically, larger
of Bi2S3, such particles are in fact layers of the semi- fibers were obtained in ethyleneglycol and the dimen-
conductor. In this case, and as suggested in Figure 4, sions of the fibers increased as the temperature was
the TEM images agree with the presence of Bi2S3 raised. For example, the TEM image in Figure 5 shows
nanocrystals with a linear dimension for which quan- Bi2S3 nanoparticles (ca. 24-nm linear cross section)
tum size effects are expected to be observed. It also prepared in ethyleneglycol (197 °C) using the single-
seems that such quantum size effects are observed, even molecule precursor [Bi(S2CNMenHex)3(C12H8N2)] (2).
though the length of the particles, the largest linear Longer fibers were obtained using this precursor, when
dimension, surpasses the nanosize regime. In this compared to the use of precursor 1, although a similar
context it is noteworthy that quantum size effects have morphology was observed, providing the solvent and the
also been reported by Variano et al. for Bi2S3 disklike- temperature were maintained. The thermal analysis of
shaped particles prepared in microemulsions, for which the molecular precursors 1 and 2 showed that both
the anisotropic particle-in-a-box model has been ap- compounds thermally decompose in one step. The lower
temperature of decomposition of 2 (280 °C), when
(40) Peterson, M. W.; Micic, O. I.; Nozik, A. J. J. Phys. Chem. 1988,
92, 4160.
(41) Wilcoxon J. P.; Samara, G. A. Phys. Rev. B 1995, 51, 7299. (42) Brus, L. E. J. Chem Phys. 1984, 80, 4403.
2110 Chem. Mater., Vol. 13, No. 6, 2001 Monteiro et al.

compared to 1 (300 °C), may account for such slight

differences in the particles size, although the precursors’
thermal stabilities are not so pronounced as to lead to
a strong influence on the final morphology of the Bi2S3
nanocrystals. On the other hand, the influence of the
solvent and temperature on the morphology of the
powders was also clearly evident by SEM performed on
the nondispersible solid phases collected from the ther-
malysis of the molecular precursors. Figure 6 shows the
SEM images of such powders, which have been prepared
in p-xylene (a), 2-ethoxyethanol (b), 4-ethylpyridine (c),
and TOPO (d). The predominance of fiber-type particles
is again observed in all the samples with the exception
of the one prepared in TOPO in which elemental
bismuth was also present. For this sample, the elemen-
tal bismuth particles were also analyzed by TEM and
transmission electron diffraction, performed on the
dispersible powders (nanophase material), showing
either a hexagonal or spherical shape. When p-xylene
is used, which is a noncoordinating solvent, steric
hindrance of the particles is less effective and hence
agglomerates of smaller particles have been formed, as
discussed above (Figure 6a).
Bismuth(III) sulfide crystallizes in a layer structure
formed from threadlike molecules. The crystallization
occurs in a two-dimensional array forming infinite
bands, which are connected via weaker van der Waals
interactions. The Bi2S3 fiber-type morphology observed
for the powders may result from the cleavage of larger
particles from the van der Waals planes of the crystal-
line structure or/and from preferential directional growth
of the particles. In fact, both processes have been
reported to occur for Bi2S3 particles grown using distinct
synthetic methods.43,44 Temperature exerts a strong
influence on the morphology of particles in which
preferential growth is a relevant process and this
experimental parameter was investigated for the solvent
ethyleneglycol. As shown in Figure 7, distinct morphol-
ogies for micrometric Bi2S3 particles were obtained
depending on the temperature used, 132 and 197 °C.
Such SEM images suggest that the morphological
evolution of the particles is to obtain longer fibers as
the temperature increases, which may result from a
higher growth rate along the c axis. Solvent thermalysis
of commercial Bi2S3 over 2 h, using similar conditions
to those used in the synthesis of the nanocrystalline Figure 7. SEM images of submicrometric Bi2S3 particles
counterpart, did not lead to fiber-type particles. It has prepared in ethyleneglycol at (a) 132 and (b) 197 °C (bar )
0.3 µm).
been reported that treatment of macrocrystalline lamel-
lar semiconductors (e.g., MoS2, WS2, Bi2Se3) in aceto-
a chemical vapor deposition method in which the
nitrile results in stable nanodispersed systems.45 The
molecular precursors used were similar to those em-
breakup of crystallites due to interpenetration of aceto-
ployed in this work.22 Therefore, it is suggested that the
nitrile molecules within the van der Waals planes has
Bi2S3 fiber-type morphology for particles prepared from
been suggested as the underlying mechanism. The Bi-S
the decomposition of bismuth(III) dithiocarbamato com-
interatomic distance at the van der Waals planes is ca.
plexes is mainly a result of preferential directional
300 pm; hence, an exfoliation process by intercalation
growth along the c axis, the shortest distance of the unit
of larger molecules, such as those of the solvents used
cell of bismuthinite.
in this work, seems unlikely. Moreover, the fiber-type
morphology has been observed by us for Bi2S3 particles
prepared using several chemical strategies, including 4. Conclusions

(43) Mizoguchi, H.; Hosono, H.; Ueda, N.; Kawazoe, H. J. Appl.

Phys. 1995, 78, 1376. It was shown that crystalline Bi2S3 nano- and micro-
(44) Yu, S.; Shu, L.; Yang, J.; Han, Z.; Qian, Y.; Zhang, Y. J. Mater. particles showing well-defined morphologies can be
Res. 1999, 14, 4157.
(45) Comor, M. I.; Dramicanin, M. D.; Rakocevic, Z.; Zec, S.; prepared using the solution-phase thermalysis of bis-
Nedeljkovic, J. M. J. Mater. Sci. Lett. 1998, 17, 1401. muth(III) alkyldithiocarbamato complexes. The tem-
Dialkyldithiocarbamato Complexes of Bismuth(III) Chem. Mater., Vol. 13, No. 6, 2001 2111

perature and chemical nature of the solvent used have Professor Paul O’Brien (University of Manchester) for
a strong influence on the final properties of the powders. helpful discussions.
Particle growth along the c axis appears to be a
Supporting Information Available: Crystal data and
preferential process leading to Bi2S3 particulates in structure refinement, atomic coordinates and equivalent iso-
which the fiber-type morphology is predominant. tropic displacement parameters, bond lengths and angles,
anisotropic displacement parameters, hydrogen coordinates
Acknowledgment. We thank Fundação para a and isotropic displacement parameters, and structures of
Ciência e a Tecnologia (FCT) (Project POCTI/1999/CTM/ compounds 1 and 2 (PDF). This material is available free of
charge via the Internet at http://pubs.acs.org.
35458). O.C.M. thanks FCT for a Ph.D. grant. We thank
Mr. A. Lopes for his expertise on the TEM analysis and CM000973Y