A luminescent silver-saccharinato complex with S,S-diphenylsulfimide: Synthesis, spectroscopic, thermal, structural and DFT computational studies

Article abstract of DOI:10.1016/j.molstruc.2006.05.053

A new silver(I)-saccharinato (sac) complex with S,S-diphenylsulfimide, [Ag(sac)(Ph₂SNH)], has been prepared and characterized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X-ray diffraction. X-ray diffraction analyses show that the title complex has a monomeric structure containing linearly coordinated silver(I) ion with an N-Ag-N angle of 173.80(10)°. The individual molecules are linked by strong N-H?O hydrogen bonds and aromatic stacking π?π interactions and packing of the molecules is further reinforced by C-H?π interactions. Ph₂SNH and [Ag(sac)(Ph₂SNH)] in solution at room temperature display intense blue luminescence with emission maxima at 380 and 408 nm, respectively. The photoluminescence properties have been investigated by DFT calculations, showing that the luminescence properties of the Ph₂SNH are due to intraligand transitions, while for the silver(I) complex, the luminescence was originated from several transitions including intraligand transitions and metal-to-ligand charge transfer (MLCT).

Full text of DOI:10.1016/j.molstruc.2006.05.053

Journal of Molecular Structure 828 (2007) 181–187
www.elsevier.com/locate/molstruc
A luminescent silver-saccharinato complex with
S,S-diphenylsulfimide: Synthesis, spectroscopic, thermal, structural
and DFT computational studies
a
b
b,
c
Sedat Gumus , Sevim Hamamci , V.T. Yilmaz *, Canan Kazak
a
Department of Physics, Education Faculty, Ondokuz Mayis University, 05189 Amasya, Turkey
Department of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayis University, 55139 Kurupelit, Samsun, Turkey
b
c
Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayis University, 55139 Kurupelit, Samsun, Turkey
Received 17 February 2006; received in revised form 29 May 2006; accepted 31 May 2006
Available online 14 July 2006
Abstract
A new silver(I)-saccharinato (sac) complex with S,S-diphenylsulfimide, [Ag(sac)(Ph2SNH)], has been prepared and characterized by
elemental analysis, IR spectroscopy, thermal analysis and single crystal X-ray diffraction. X-ray diffraction analyses show that the title
complex has a monomeric structure containing linearly coordinated silver(I) ion with an N–Ag–N angle of 173.80(10)ꢀ. The individual
molecules are linked by strong N–Hꢀ ꢀ ꢀO hydrogen bonds and aromatic stacking pꢀ ꢀ ꢀp interactions and packing of the molecules is fur-
ther reinforced by C–Hꢀ ꢀ ꢀp interactions. Ph2SNH and [Ag(sac)(Ph2SNH)] in solution at room temperature display intense blue lumines-
cence with emission maxima at 380 and 408 nm, respectively. The photoluminescence properties have been investigated by DFT
calculations, showing that the luminescence properties of the Ph2SNH are due to intraligand transitions, while for the silver(I) complex,
the luminescence was originated from several transitions including intraligand transitions and metal-to-ligand charge transfer (MLCT).
ꢁ 2006 Elsevier B.V. All rights reserved.
Keywords: Silver(I); Saccharin; S,S-Diphenylsulfimide; Luminescence, DFT calculations
1. Introduction
of its imino nitrogen, carbonyl oxygen, or sulfonyl oxygen
atoms, exhibiting different coordination modes such as
monodentate (through the N– or the carbonyl O–atom),
bidentate (N, O), tridentate (N, O, O) or bridging forming
[2]. Recently, we started a research project to prepare
mixed-ligand silver(I) complexes of sac and the studies
have generated a wide range of silver(I) complexes with
monomeric, dimeric, tetrameric and polymeric structures
[3]. Among them, [Ag2(sac)2(aeprd)2] (aeprd = N-(2-ami-
noethyl)pyrrolidine) was found to be luminescent at room
temperature [3i]. As a continuation of this study, in this
work, we used a relatively bulky ligand, S,S-diphenylsulfi-
mide (Ph2SNH), which was shown to form interesting com-
plexes with various metal ions [4], and this paper reports
the synthesis of the first example of a S,S-diphenylsulfimide
complex of silver(I) with sac, namely [Ag(sac)(Ph2SNH)].
The crystal structure of this complex was determined by
single-crystal X-ray diffraction. It has also been
The water soluble alkali and Earth-alkali salts of
saccharin (also called 2,3-dihydro-3-oxobenzisosulfonaz-
ole; 1,2-benzisothiazoline-3-(2H)one 1,1-dioxide or o-ben-
zosulfimide) are widely used as a commercially available
non-caloric artificial sweetener and food additive. Saccha-
rin, itself, does not coordinate metal ions, but its deproto-
nated form (saccharinate) interacts with trace elements in
human body and readily forms complexes with a large
number of metal ions [1].
We have long been interested in the coordination
chemistry of the saccharinate anion (sac) since sac acts a
polyfunctional ligand and may bond to metals by means
*
Corresponding author. Tel.: +90 362 312 1919; fax: +90 362 457 6081.
E-mail address: vtyilmaz@omu.edu.tr (V.T. Yilmaz).
0022-2860/$ - see front matter ꢁ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2006.05.053

182
S. Gumus et al. / Journal of Molecular Structure 828 (2007) 181–187
characterized by elemental analysis, thermal, and spectro-
scopic techniques. Furthermore, the spectral and optical
properties of [Ag(sac)(Ph2SNH)] were also studied by
DTF calculations.
hydrogen atoms were easily found from the difference
Fourier map and refined anisotropically. All CH hydro-
gen atoms were included using a riding model, while
the NH hydrogen atom was refined freely. Molecular
graphics were prepared using ORTEP3 [6]. Details of
crystal data, data collection, structure solution and
refinement are given in Table 1.
NH
S
O
C
S
O
2.4. Computational method
O
N
DFT calculations are carried out with the GAUSSIAN
03 program [7]. The DFT-B3LYP level was used for both
geometry optimization and frequency calculations. The 6-
31G** method was used for the Ph2SNH molecule. The
basis set LANL2DZ and the corresponding Los Alamos
relativistic effective core potential were employed to consid-
er account scalar relativistic effects, including mass velocity
and Darwin corrections for the heavy silver atom, while the
6-31G* basis set was applied to the non-metal atoms in the
silver(I) complex.
The ground-state geometries were obtained in the gas
phase by full geometry optimization, starting from the
structural data without any symmetry constraints. The
orbital shapes were visualized using GAUSSIAN VIEW
03 software [8]. The calculated vibrational frequencies are
scaled by 0.9614 [9].
sac
Ph2SNH
2. Experimental
2.1. Materials and instrumentation
All reagents were commercially obtained and used with-
out any further purification. Thermal analysis curves (TG
and DTA) were obtained using a Rigaku TG8110 thermal
analyzer in a static air atmosphere at a heating rate of
10 ꢀC minꢁ1. Elemental analyses were performed by a
Vario EL elemental analyzer for C, H, N and S. FT–IR
spectra were measured on a JASCO FT/IR–430 spectro-
photometer (KBr pellets) in the 4000–400 cmꢁ1 range.
Electronic spectra of 1 · 10ꢁ2 M solutions in a 9:1 (v:v)
CH2Cl2 and acetonitrile mixture were measured with a
Unicam UV2 100 spectrophotometer. Excitation and emis-
sion spectra were recorded at concentrations of 1 · 10ꢁ3 M
in a 9:1 (v:v) mixture of dichloromethane and acetonitrile
at room temperature with a Perkin Elmer-LS50B spectro-
photometer. DFT calculations were performed by using
GAUSSIAN 03 program.
Table 1
Crystallographic data and structure refinement for [Ag(sac)(Ph2SNH)]
[Ag(sac)(Ph2SNH)]
Formula
C19H15N2 O3S2Ag
Molecular weight
Temperature
Wavelength
Crystal system
Space group
491.32
100(2) K
0.71069 A
Monoclinic
P21/n
˚
2.2. Synthesis of [Ag(sac)(Ph2SNH)]
Unit cell dimensions
a (A)
˚
10.938(2)
14.472(3)
12.119(2)
108.27(1)
˚
b (A)
Solid Na(sac) Æ 2H2O (1 mmol, 0.24 g) was mixed with a
solution of AgNO3 (0.17 g, 1 mmol) dissolved in 5 ml dis-
tilled water and then, a white polycrystalline precipitate
formed. The precipitate was dissolved by adding 20 ml
CH2Cl2, and Ph2SNHÆH2O (1 mmol, 0.22 g) was added to
the solution and stirred for 30 min at room temperature.
The resulting solution was allowed to stand in darkness at
room temperature. Colorless crystals of [Ag(sac)(Ph2SNH)]
were obtained after two weeks. Yield 89%. Anal. Calcd. for
C19H15N2O3S2Ag (%) C, 46.45; H, 3.08; N, 5.70; S, 13.05.
Found: C, 46.63; H, 3.24; N, 5.56; S, 13.22%.
˚
c (A)
b (ꢀ)
3
˚
Volume (A )
1821.7(6)
4
1.791
1.359
Z
Calculated density (g/cm3)
l (mmꢁ1
F(000)
)
984
Crystal size (mm3)
0.52 · 0.39 · 0.14
2.26 to 26.00
ꢁ13 6 h 6 13
ꢁ17 6 k 6 17
ꢁ14 6 l 6 14
10889
h range (ꢀ)
Index ranges
Reflections collected
2.3. X-ray crystallography
Independent reflections
Reflections observed (>2sigma)
Absorption correction
Max. and min. transmission
Data/parameters
3578 [Rint = 0.0401]
3248
Numerical
0.756 and 0.593
3578/248
The data collection was performed at 100 K on a
Stoe-IPDS-2 diffractometer equipped with a graphite
monochromated Mo-Ka radiation (k = 0.71069 A). The
˚
Goodness-of-fit on F2
1.035
structures were solved by direct methods using
SHELXS-97 [5] and refined by a full-matrix least-squares
procedure using the program SHELXL97 [5]. All non-
Final R indices [I > 2sigma(I)]
R1 = 0.0292
wR2 = 0.0672
2.158 and ꢁ0.554
ꢁ3
˚
Largest diff. peak and hole (e.A
)

S. Gumus et al. / Journal of Molecular Structure 828 (2007) 181–187
183
Table 2
Selected bond lengths (A) and angles (ꢀ) for [Ag(sac)(Ph2SNH)]
3. Results and discussion
˚
Experimental
Calculated
3.1. Synthesis
Ag1–N1
Ag1–N2
2.085(2)
2.069(3)
2.112
2.163
The title silver(I) complex was readily prepared by the
direct reaction of equimolar mixture of AgNO3 and Na(sa-
c)Æ2H2O in the presence of Ph2SNH at room temperature
and obtained in high yield ca. 90%. The analytical data
(C, H, N and S) are consistent with the calculated data,
and X-ray crystal structure analysis also confirms the
chemical formulation of the complex. The title complex is
non-hygroscopic and stable in air at ambient temperatures.
It is soluble only in CH2Cl2 and melts at 207 ꢀC with
decomposition.
N2–S2
C8–S2
C14–S2
N1–Ag1–N2
N2–S2–C8
N2–S2–C14
C8–S2–C14
1.586(3)
1.794(3)
1.795(3)
173.80(10)
107.83(14)
108.72(14)
99.61(14)
1.639
1.817
1.817
168.20
107.33
110.54
102.20
Hydrogen bonds
D–Hꢀ ꢀ ꢀA
d(D–H)
0.81(4)
d(Hꢀ ꢀ ꢀA)
d(Dꢀ ꢀ ꢀA)
<(DHA)
163(3)
N2–H2Aꢀ ꢀ ꢀO3i
2.64(4)
3.426(4)
Symmetry transformations used to generate equivalent atoms: (i) = 3/
2 ꢁ x, 1/2 + y, 1/2 ꢁ z.
3.2. Crystal structure
The molecular structure of [Ag(sac)(Ph2SNH)] with the
atom labeling is shown in Fig. 1a. The selected bond
lengths and angles together with hydrogen bonding geom-
etry are collected in Table 2. The complex crystallizes in the
monoclinic space group P21/n. The silver(I) ion is coordi-
nated by a sac ligand and a Ph2SNH ligand, forming a
slightly distorted linear AgN2 motif with an N–Ag–N angle
of ca. 174ꢀ. Both Ag–N bond distances are almost identi-
˚
cal. The Ag–Nsac bond distance of 2.085(2) A is also similar
to those found in reported silver(I)-sac complexes [3,10],
but significantly shorter than the corresponding distances
˚
reported for [Ag(sac)(PPh3)2] 2.285(8) A [11] and
a
˚
[Ag2(sac)2(l-aepy)2] 2.449(2) A [3f].
C18
C17
The rings of sac (A = C1–C7, N1, S1) and Ph2SNH
(B = C8–C13 and C = C14–C19) ligands are essentially
planar and the dihedral angles of A/B, A/C, and B/C are
66.82(8), 66.93(8) and 86.80(8)ꢀ, respectively. As will be
seen in Fig. 1b, the individual molecules of
Ag(sac)(Ph2SNH)] are connected by the N–Hꢀ ꢀ ꢀO hydro-
gen bonds involving the sulfimide N–H group and sulfonyl
O atoms. The hydrogen bonded molecules also interact
with each other via aromatic p(Ph2SNH)ꢀ ꢀ ꢀp(Ph2SNH)
C19
O1
C7
C2
C16
C15
C3
C14
S2
C1
C6
Ag1
N1
N2
C4
C8
C13
C12
C5
S1
O3
O2
C9
i
˚
stacking
interactions
½Cg ꢀ Cg ¼ 3:831ð2ÞA; i ¼
C11
C10
1=2 þ x; 1=2 ꢁ y; 1=2 þ zꢂ. The intermolecular interactions
are further reinforced by four of C–Hꢀ ꢀ ꢀp interactions
involving all phenyl groups.
b
3.3. FT–IR spectra
c
Selected spectral data for [Ag(sac)(Ph2SNH)] are given
in Table 3, together with the data obtained from DFT cal-
culations. The absorption band centered at ca. 3260 cmꢁ1
is assigned to the m(NH) vibration of the N–H group and
shifted to the low frequency region by about 75 cmꢁ1, com-
pared to the free Ph2SNH ligand, due to both the coordina-
tion to silver(I) and participation in hydrogen bonding.
The relatively weak band around 3050 cmꢁ1 is attributed
to the absorption of the aromatic CH hydrogens. The
sharp band at 1645 cmꢁ1 is due to the vibration of the car-
bonyl group of the sac ligand and well accorded with those
of N-coordinated sac complexes (1650 cmꢁ1) [12]. The sym-
metric (ms) and asymmetric (mas) stretching modes of the
CNS moiety of the sac ligands appeared at approximately
1335 and 960 cmꢁ1, respectively, while the mas and ms
stretchings of the SO2 group are observed as two strong
O
a
Fig. 1. (a) Molecular structure of [Ag(sac)(Ph2SNH)] with atom-labeling
scheme and thermal ellipsoids at the 50% probability level. (b) View of the
crystal packing of [Ag(sac)(Ph2SNH)]. All C–H hydrogen atoms omitted
for clarity.

184
S. Gumus et al. / Journal of Molecular Structure 828 (2007) 181–187
Table 3
3.5. Optical properties
Experimental IR spectral dataa for [Ag(sac)(Ph2SNH)], compared with the
theoretical IR data obtained from DFT calculations
The electronic spectra of [Ag(sac)(Ph2SNH)] and the
corresponding ligands are illustrated in Fig. 3. The sac
ion in the aqueous solution exhibits two main absorption
bands at kmax = 232 nm (e = 384 Mꢁ1 cmꢁ1) and 260 nm
(e = 263 Mꢁ1 cmꢁ1), similar to the intra-ligand transitions
measured in the methanolic solution of Na(sac) Æ 2H2O
[14], while the Ph2SNH molecule displays four bands at
Assignment
Experimental
Calculated
m(N–H)
m(C–H)
m(C@O)
m(CC)
ms(CNS)
mas(SO2)
ms(SO2)
mas(CNS)
m(S@N)
m(Ag–N)
a
3261sb
3053w
1645vs
1585s, 1442s
1333m
1290s, 1255vs
1147vs
970vs, 951s
839m
3309
3066
1663
1583-1429
1328
1253
1111
917, 913
840
513, 473
k
max = 230 nm
(e = 414 Mꢁ1 cmꢁ1),
240 nm
(e =
405 Mꢁ1 cmꢁ1), 250 nm (e = 376 Mꢁ1 cmꢁ1) and 302 nm
(e = 300 Mꢁ1 cmꢁ1).
[Ag(sac)(Ph2SNH)] show two main absorptions at kmax
The
electronic
spectra
of
=
(e =
461w
Frequencies in cmꢁ1. b, broad; m, medium; w, weak; vw, very weak;
vs, very strong; s, strong; sh, shoulder.
278 nm and 300 nm
(e = 340 Mꢁ1 cmꢁ1
)
325 Mꢁ1 cmꢁ1) for sac and Ph2SNH species, respectively,
and the band at kmax = 242 nm (e = 422 Mꢁ1 cmꢁ1) is
due to both sac and Ph2SNH absorptions. It may be noted
that an approximately 10 nm red-shift occurred for the
absorption bands of both ligands centered at around
230 nm, and furthermore, for the sac ligand, the band at
260 nm was shifted to 278 nm in the complex upon
coordination.
IR bands at ca.1255 and 1147 cmꢁ1, respectively. The
vibration of the m(S@N) group in the free Ph2SNH mole-
cule is found at 991 cmꢁ1, but shifted to 839 cmꢁ1 in the sil-
ver(I) complex.
3.4. Thermal behavior
The sac ion is not luminescent, but the free Ph2SNH mol-
ecule in solution displays a broad emission band at 408 nm
followed by a low intensity band at 484 nm upon excitation
at 220 nm (see Fig. 4). Both emission bands may be assigned
to the n–p* or p–p* transitions. Commonly, silver(I) com-
plexes have been found to emit weak photoluminescence at
low temperature [15] and only a few silver(I) complexes
exhibit luminescence at room temperature [3i,16]. The lumi-
nescence spectra of [Ag(sac)(Ph2SNH)] in solution at room
temperature are shown in Fig. 4. The excitation spectrum
of the complex shows two maxima at 215 and 284 nm,
while the complex exhibits an intense blue photolumines-
cence with four emission maxima at 380, 420, 487 and
532 nm upon excitation at 215 nm. The emission of the silver
Thermal decomposition behavior of both complexes
was studied by thermogravimetric (TG) and differential
thermal (DTA) analyses in a static atmosphere of air.
The TG and DTA curves in Fig. 2 show that the com-
plex decomposes in two distinct stages. The endothermic
removal of the Ph2SNH ligand takes place between 209
and 325 ꢀC with a mass loss of 40.72% (calcd. 40.97%),
while the degradation of the sac anion occurs in the tem-
perature range 330–506 ꢀC with two violently exothermic
peaks at 460 and 480 ꢀC, which are characteristic for the
decomposition of sac complexes [13]. The experimental
mass loss of 37.34% is in very good agreement with
the calculated mass loss of 37.08%. The decomposition
process ends at around 510 ꢀC, giving a final decomposi-
tion product of metallic silver (Total mass loss: found
78.06% and calcd. 78.05%).
100
TG
60
DTA
20
200
300
400
20
200
400
600
Wavelenght, nm
Temperature, oC
Fig. 3. Electronic spectra of sac ( - - - -), Ph2SNH (ꢀ ꢀ ꢀꢀ ꢀ ꢀ), and
Fig. 2. Thermal analysis curves of [Ag(sac)(Ph2SNH)].
[Ag(sac)(Ph2SNH)] (——). Note that the spectra are not in scale.

S. Gumus et al. / Journal of Molecular Structure 828 (2007) 181–187
185
mental and computational data in Table 2 clearly show
that both data only slightly differ from each other. For
example, the largest difference between experimental and
Ex
Em
˚
calculated Ag–N length is about 0.09 A, while the biggest
deviation occurs in the N–Ag–N angle by ca. 6ꢀ. As a result
it may be said that the calculated geometrical parameters
represent a good approximation.
The computational IR spectral frequencies are listed in
Table 3, together with experimentally determined frequen-
cies. The NH and CH groups participate in the hydrogen
bonding and therefore, the experimental absorption bands
of these groups were found at a lower frequency. The cal-
culated carbonyl frequency of 1663 cmꢁ1 well compares
200
600
300
400
Wavelenght, nm
500
Fig. 4. Excitation and emission spectra of Ph2SNH ( - - - -) and
[Ag(sac)(Ph2SNH)] (——) in a 9:1 (v:v) mixture of CH2Cl2 and acetoni-
trile at room temperature.
with the experimentally determined value of 1645 cmꢁ1
,
since the carbonyl group of sac does not participate in
any intermolecular interaction. As observed earlier [3i],
the computational frequencies of the CNS and SO2 groups
of the sac ligand were somewhat low, compared to experi-
mentation. The experimental values of the S@N band of
the Ph2SNH moiety agree very well with the calculated val-
ue. Although the experimental frequency value of 461 cmꢁ1
seems to be significantly high for such a vibration between
silver and the N donor bulky ligands, the assignment of the
experimental m(Ag–N) vibration is based on the theoretical-
ly calculated frequencies. Both calculated and experimental
frequencies are found to be in agreement, and consistent
with the frequency value (476 cmꢁ1) of a linear silver com-
plex [Ag(NH3)2]2SO4 [17].
(I) complex is much more intense and covers a broader spec-
tral range, compared to that of the free Ph2SNH molecule.
The bands at 420 and 487 nm resemble the transition bands
observed for the Ph2SNH molecule, with a slight red-shift,
while the low-energy emission band at 532 nm is expected
to be the metal-to-ligand charge transfer (MLCT). As will
be discussed later, the main high-energy emission band at
380 nm may be originated from a ligand-based n–p* or
p–p* process, probably induced by the silver(I) ion.
3.6. DFT calculations
The calculated structural parameters are listed in Table
2. The significant number is maintained to be four, which is
sufficient for one bond length to be differentiated from the
other. It should be noted that the experimental data belong
to solid phase, whereas the calculated data correspond to
the isolated molecule in gas-phase. However, the experi-
In order to assign the emission bands, molecular orbital
(MO) calculations were also performed, and the calcula-
tions indicate that Ph2SNH and [Ag(sac)(Ph2SNH)] have
53 and 109 occupied MOs, respectively. Fig. 5 shows the
highest occupied molecular orbital (HOMO) and the low-
est unoccupied molecular orbital (LUMO) for Ph2SNH
Fig. 5. Frontier molecular orbitals for Ph2SNH and [Ag(sac)(Ph2SNH)].

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S. Gumus et al. / Journal of Molecular Structure 828 (2007) 181–187
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molecule and the silver(I) complex. As will be seen in
Fig. 5, the HOMO of the title complex is principally delo-
calized among the N atom and three O atoms of the sac
ligand and also associated with the silver(I) center (namely
the d2z orbital). It may be said that the HOMO is mainly
composed of r(Ag–Nsac) orbital, whereas the LUMO is
localized on all the atoms of the Ph2SNH ligand excluding
the silver(I) ion, indicating that the LUMO is mostly the p-
antibonding type orbital. For Ph2SNH, the HOMO is asso-
ciated with the N, S and some C atoms of the phenyl rings,
whereas the LUMO is mainly of the p-antibonding charac-
ter. The values of the energy separation between the HOMO
and LUMO in Ph2SNH and [Ag(sac)(Ph2SNH)] were found
to be identical, and calculated as 0.165 a.u. (4.47 eV), which
are much bigger than the experimentally measured emission
energy values of 3.04 eV (408 nm) and 3.27 eV (380 nm),
respectively. The deviation between experimentation
and computation may be due to the ground-state
considerations in the DFT calculations, and the intermolec-
ular interactions and solvent effects in the solution.
According to the literature, the emission bands in the
reported silver(I) complexes originate from dr*-pr or 4d-
5s transitions and the excited states of MLCT or MMLCT
[18]. The results of the present study show that for the sil-
ver(I) complex, the high-energy emission bands can mainly
be assigned to intraligand transitions, whereas the low-en-
ergy emission transition is expected to be the MLCT and it
has been suggested that the photoluminescence of the sil-
ver(I) complex is the cooperative association of the intral-
igand and MLCT transitions.
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4. Supplementary data
Crystallographic data for the structure reported in this
paper have been deposited with the Cambridge Crystallo-
graphic Data Centre as the supplementary data, CCDC
No. CCDC 297772. Copies of the data can be obtained,
free of charge, on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: +44 1223 336033 or e-mail:
deposit@ccdc.cam.ac.uk).
Acknowledgements
The authors are grateful to the Research Fund of Ond-
okuz Mayis University (Project No. F365) for financial
support of this work. We also thank Prof. Dr. M. Volkan
and Research Assistant S. Surdem, for their assistance in
obtaining the luminescence spectra.
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