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Synthesis and optical properties of two novel chlorobismuthate(III)

complexes: [8-Hydroxyquinolinium]
4
K
2
[BiCl
6
]
2
6H
2
O (1)
and [8-hydroxyquinolinium]
6
[Bi
2
Cl
10
][BiCl
5
(H
2
O)]6H
2
O(2)
Yong-Jing Wang
a,b
, Li Xu
a,
*
a
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science,
Fuzhou, Fujian 350002, China
b
Graduate School of the Chinese Academy of Sciences, Beijing 100039, China
Received 12 April 2007; received in revised form 13 June 2007; accepted 13 June 2007
Available online 20 June 2007
Abstract
Two novel chlorobismuthate(III) complexes [8-hydroxyquinolinium]
4
K
2
[BiCl
6
]
2
6H
2
O (1) and [8-hydroxyquinolinium]
6
[Bi
2
Cl
10
]
[BiCl
5
(H
2
O)]6H
2
O (2) have been synthesized in solution and characterized by single-crystal X-ray diraction. The structure of 1 contains
1-D inorganic zigzag chains formed by BiCl
6
octahedra and KCl
4
O
3
decahedra with organic 8-hydroxyquinolinium cations binding
through KO bonds or H-bonds. And compound 2 has two dierent anionic units of [Bi
2
Cl
10
]
4
and [BiCl
5
(H
2
O)]
2
. IR, UVvis DRIS,
and uorescent spectra of two compounds were studied.
2007 Elsevier B.V. All rights reserved.
Keywords: Chlorobismuthate(III) complex; Crystal structure; Photoluminescence
1. Introduction
Bismuth complexes have been studied intensively over
the last few decades due to their interesting photochemistry
and photophysics properties caused by active lone pairs
[1]. In recent years, a great variety of dierent halobismuth-
ato(III) anionic complexes have been investigated by X-ray
analysis and most of them are constituted by polynuclear
anions with dierent polymerization geometries where the
basic MX
6
octahedra share corners, edges, and faces
[28]. Some special types of the anionic structure usually
show ferroelectricity [912]. In this respect, interest has
been focused on the role of the charge, size, and shape of
the counter-cation in promoting the selfassembly of a char-
acteristic anionic polynuclear species [13]. In addition, the
occurrence of anionanion interactions, usually of the type
NH
cation
. . .X
anion
inuence the crystal paking.
In the previous work, Bombieri et al. have reported the
structures of quinolinium, isoquinolinium and 8-hydroxy-
quinolinium polychlorobismuthate derivatives and dis-
cussed the inuence of the organic cations to the
geometries of the anions [14]. In this work, we also use the
protonated 8-hydroxyquinolinin as the cation and obtained
two novel chlorobismuthate(III) complex salt [8-hydroxy-
quinolinium]
4
K
2
[BiCl
6
]
2
6H
2
O (1) which possesses a one-
dimensional structure and mixed organicinorganic cations,
and [8-hydroxyquinolinium]
6
[Bi
2
Cl
10
][BiCl
5
(H
2
O)]6H
2
O
(2) which has two dierent anionic units of [Bi
2
Cl
10
]
4
and
[BiCl
5
(H
2
O)]
2
. In addition, the IR, UVvis DRIS, and
uorescent spectra of the title compounds have also been
investigated.
2. Experimental
2.1. Physical measurements
All reagents were purchased commercially and used
without further purication. Elemental analyses (C, H,
0022-2860/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2007.06.003
*
Corresponding author.
E-mail address: yongjing_wang@fjirsm.ac.cn (L. Xu).
www.elsevier.com/locate/molstruc
Available online at www.sciencedirect.com
Journal of Molecular Structure 875 (2008) 570576
and N) were performed on a Perkin-Elmer 2400 CHN Ele-
mental Analyzer. X-ray powder diraction (XRD) of the
samples were collected on a PANalytical X Pert PRO dif-
fractometer with Cu Ka radiation (45 kV, 40 mA) in the
continuous scanning mode. The 2h range used was from
10 to 50 in steps of 0.04 with a count time 1 s. The IR
spectra were recorded in the 4000400 cm
1
region by
using KBr pellet on a Nicolet Magna 750FT-IR spectro-
photometer. The UVvis DRIS spectra were recorded on
a Perkin-Elmer Lambda 900 UVvis spectrometer. The
uorescent spectra of compound 1 were measured on an
Edinburgh Instrument F920 uorescent spectrometer using
Xe lamp in the solid state at room temperature.
2.2. Synthesis
2.2.1. Synthesis of [8-hydroxyquinolinium]
4
K
2
[BiCl
6
]
2
6H
2
O
(1)
The compound 1 was prepared by following synthetic
procedure: Bi
2
O
3
(1 mmol) dissolved in hot 6 M HCl
(15 ml) was treated with 8-hydroxyquinoline (2 mmol) also
dissolved in hot 6 M HCl (5 ml), then 2 ml 10 M KOH
solution was added dropwise. After heating to 90 C for
10 min, the solutions were ltered and allowed to evaporate
at room temperature until the light yellow prismatic crys-
tals of compound 1 were form with about 40% yield based
on bismuth. Anal. Calcd. for C
36
H
44
N
4
Cl
12
O
10
K
2
Bi
2
: C,
26.76; N, 3.47; H, 2.73. Found: C, 26.58; N, 3.42; H,
2.54%. IR (KBr cm
1
): 3485, 3215, 3077 1634, 1603,
1562, 1419, 1397, 1311, 1091, 884, 878, 761, 614, 576,
490 cm
1
.
2.2.2. Synthesis of [8-hydroxyquinolinium]
6
[Bi
2
Cl
10
] [BiCl
5
-
(H
2
O)]6H
2
O (2)
A solution of 8-hydroxyquinoline (0.2 mmol) in acetone
(5 ml) was added to a solution of BiCl
3
(0.1 mmol) in ace-
tone (5 ml). After the yellow mixture was stirred overnight
the solvent was evaporated until dryness. The residue was
extracted with acetonitrile (5 ml) and was layered with
ether (5 ml). Yellow crystals forming on the wall of the
tube were obtained after 1 week. Anal. Calcd. for
C
54
H
62
N
6
Cl
15
O
13
Bi
3
: C, 29.98; N, 3.88; H, 2.86. Found:
C, 29.76; N, 3.67; H, 2.66%. IR (KBr cm
1
): 3445, 3154,
1632, 1602, 1555, 1499, 1471, 1419, 1397, 1306, 1273,
1091, 1059, 991, 884, 819, 761, 617, 576, 539, 490 cm
1
.
2.3. X-ray crystallography
Crystallographic data for two compounds was collected
on a Rigaku Mercury-CCD diractometer with MoKa
radiation (k = 0.71073 A

) by using the phi and omega scan


method at 293(2) K. The CrystalClear software package
was used for data reduction and empirical absorption cor-
rection [15]. The structure was solved by direct methods
and rened using full-matrix least-squares calculations with
anisotropic displacement parameters for all non-hydrogen
atoms. All hydrogen atoms were geometrically xed at
the calculated positions attached to their parent atoms,
and treated as riding atoms. All calculations were per-
formed using SHELXTL-97 program [16]. Crystallo-
graphic data and experimental details for structure are
list in Table 1. Selected bond lengths and bond angles are
listed in Table 2.
Powder XRD patterns of the samples used in the follow-
ing spectra analysis are in good accordance with those in
the simulated XRD powder patterns of the two com-
pounds, as shown in Fig. 1.
3. Results and discussion
3.1. Structure description
3.1.1. Structure of [8-hydroxyquinolinium]
4
K
2
[BiCl
6
]
2
6H
2
O
(1)
The crystallorgraphic analysis reveals that the crystal
structure of compound 1 consists of [BiCl
6
]
3
anions, 8-
hydroxyquinolinium cations, K
+
cation and water mole-
cules as shown in Fig. 2. The Bi
3+
cations are coordinated
by six Cl

anions with distances ranging from 2.687(3) to


2.749(10)

A
0
. The values of bond angles ClBiCl are near
Table 1
Crystal data and structure renement for compounds 1 and 2
1 2
Empirical formula C
36
H
44
N
4
Cl
12
O
10
K
2
Bi
2
C
27
H
31
N
3
Cl
7.5
O
6.5
Bi
1.5
Formula weight
(g mol
1
)
1614.32 1080.89
Temperature (K) 293(2) 293(2)
Wavelength (A

) 0.71073 0.71073
Crystal system Triclinic Monoclinic
Space group P
1
C2/c
Unit cell dimensions
a 9.155(1) 20.853(6)
b 10.608(1) 17.441(5)
c 13.998(2) 20.498(5)
a 87.52(1) 90.00
b 87.05(1) 100.199(3)
c 85.50(1) 90.00
Volume (Z) 1352.39(20), 1 7337(3), 8
D
calc
(g cm
3
) 1.982 1.957
l (mm
1
) 7.297 7.783
F(000) 776 4144
Crystal size (mm) 0.40 0.15 0.10 0.3 0.1 0.1
h range () 3.0625.03 2.3427.47
Limiting indices 7 6 h 6 10,
12 6 k 6 12
27 6 h 6 23,
22 6 k 6 22
15 6 l 6 16 26 6 l 6 22
Reections collected 8300 8387
Independent
reections
4715 [R
int
= 0.0241] 6606 [R
int
= 0.0534]
Renement method Full-matrix least-
squares on F
2
Full-matrix least-
squares on F
2
GOF 1.010 1.0908
Final R indices [I > 2r
(I)]
R
1
= 0.0275
wR
2
= 0.0761
R
1
= 0.0534
wR
2
= 0.1115
R indices (all data) R
1
= 0.0403
wR
2
= 0.0993
R
1
= 0.0745
wR
2
= 0.1211
Largest di. peak and
hole (e A

3
)
0.781 and 1.619 2.321 and 1.321
Y.-J. Wang, L. Xu / Journal of Molecular Structure 875 (2008) 570576 571
to 90 or 180, which make the [BiCl
6
]
3
octahedra more
regular. The K
+
cation is coordinated by three O atoms
(two from water molecules and one from 8-hydroxyquino-
linium) with distances ranging from 2.839(15) to
2.928(12)

A
0
and to four bridging Cl

anions with distances


ranging from 3.112(19) to 3.299(22)

A
0
.
A comparison of dierent structures with chlorobismu-
tate octahedra shows the BiCl bond lengths assume dier-
ent values as depending on the number of the interaction
with the cations [14]. For instance when the cation interac-
tion is relatively strong as in [8-hydroxyquinolini-
um]
4
[BiCl
6
] Cl2H
2
O [14] with intermolecular contacts
N Cl 3.173(5), 3.178(4)

A
0
and O Cl 3.173(5)

A
0
, the cor-
responding BiCl distance is longer 2.940(2)

A
0
compared
to the shorter BiCl distance 2.547(2)

A
0
where the chlorine
is involved in rather weak interaction with a water mole-
cule (O
w
Cl 3.450(5)

A
0
). While in [(CH
3
)
2
NH
2
]
4
Cl[BiCl
6
]
[17], the chlorines are all included in weak interactions N
H Cl in the interval 3.02(2)3.57(2)

A
0
and consequentely
the range of the BiCl distances is very narrow being the
2.663(6) the lower and the 2.732(4)

A
0
the higher values.
In the present compound we nd the range of the BiCl
distances is also rather narrow because the organic cations
interact the chlorobismutate anions only with weak inter-
molecular H-bonds OH Cl 3.092(12)

A
0
.
The structure of 1 is based on 1-D inorganic zigzag
chains that are formed by alternating BiCl
6
octahedron
Fig. 1. Powder XRD patterns of the samples are similar with the
simulated XRD powder patterns.
Table 2
Selected bond lengths (A

) and angles (
o
) for compounds 1 and 2
Compound 1
K(1)OW(2) 2.839(15) K(1)Cl(6) 3.200(6)
K(1)OW(3) 2.849(18) K(1)Cl(4) 3.247(20)
K(1)O(1) 2.928(12) K(1)Cl(1)#1 3.299(22)
K(1)Cl(2) 3.112(19)
Bi(1)Cl(6) 2.694(3) Bi(2)Cl(3) 2.687(3)
Bi(1)Cl(4) 2.70(1) Bi(2)Cl(2) 2.695(9)
Bi(1)Cl(5) 2.737(8) Bi(2)Cl(1) 2.749(10)
OW(2)K(1)OW(3) 139.97(12) Cl(3)Bi(2)Cl(3)#1 179.99(5)
OW(2)K(1)O(1) 65.15(13) Cl(3)Bi(2)Cl(2) 91.08(5)
OW(2)K(1)Cl(2) 78.38(9) Cl(3)Bi(2)Cl(1) 90.73(5)
OW(3)K(1)Cl(2) 115.4(1) Cl(2)#1Bi(2)Cl(1) 88.53(5)
OW(2)K(1)Cl(6) 73.27(9) Cl(2)Bi(2)Cl(1) 91.47(5)
OW(3)K(1)Cl(6) 128.86(10) Cl(6)#2-Bi(1)Cl(6) 180.00(5)
OW(2)K(1)Cl(4) 139.74(10) Cl(6)Bi(1)Cl(4) 87.01(5)
O(1)-K(1)Cl(4) 117.59(10) Cl(6)Bi(1)Cl(5) 91.86(5)
OW(3)K(1)Cl(1)#1 75.37(9) Cl(4)Bi(1)Cl(5) 89.36(5)
Cl(2)K(1)Cl(1)#1 72.63(5) Cl(4)#2-Bi(1)Cl(5) 90.64(5)
Compound 2
Bi(1)Cl(4) 2.581(2) Bi(2)Cl(9) 2.526(3)
Bi(1)Cl(2) 2.630(2) Bi(2)Cl(8)#1 2.690(2)
Bi(1)Cl(3) 2.680(2) Bi(2)Cl(8) 2.690(2)
Bi(1)Cl(6) 2.709(2) Bi(2)Cl(7) 2.709(2)
Bi(1)Cl(1) 2.872(2) Bi(2)Cl(7)#1 2.709(2)
Bi(1)Cl(5) 2.9078(19) Bi(2)O(4) 2.728(10)
Cl(4)Bi(1)Cl(5) 177.48(5) Cl(9)Bi(2)Cl(8)#1 91.33(4)
Cl(2)Bi(1)Cl(1) 172.14(7) Cl(8)#1Bi(2)Cl(7)#1 85.03(8)
Cl(3)Bi(1)Cl(6) 173.48(7) Cl(8)#1Bi(2)Cl(8) 177.33(9)
Cl(4)Bi(1)Cl(3) 85.44(7) Cl(9)Bi(2)Cl(7) 92.24(7)
Cl(6)Bi(1)Cl(5) 89.62(4) Cl(8)Bi(2)Cl(7)#1 94.87(8)
Cl(2)Bi(1)Cl(3) 89.67(7) Cl(7)Bi(2)Cl(7)#1 175.51(13)
Cl(6)Bi(1)Cl(1) 87.73(5) Cl(9)Bi(2)O(4) 180.000(1)
Cl(4)Bi(1)Cl(1) 95.25(7) Cl(8)#1Bi(2)O(4) 88.67(4)
Cl(2)Bi(1)Cl(5) 89.74(7) Cl(7)Bi(2)O(4) 87.76(7)
Cl(4)Bi(1)Cl(5) 177.48(5) Cl(9)Bi(2)Cl(8)#1 91.33(4)
Symmetry transformations used to generate equivalent atoms: For 1: #1
x+1, y, z+1; #2 x+2, y, z. For 2: #1 x, y, z+1/2.
Fig. 2. The molecular structure of the compound 1.
Fig. 3. A view of the structure of 1 along b-axis showing the 1-D zigzag
chains.
572 Y.-J. Wang, L. Xu / Journal of Molecular Structure 875 (2008) 570576
and KCl
4
O
3
decahedron in edge-sharing fashion (Fig. 3).
The 8-hydroxyquinolinium cations can be divided into
two categories: one is linked to these inorganic zigzag
chains through KO bonds while the other through inter-
molecular H-bonds. The distance between the relative
molecular planes of neighboring 8-hydroxyquinolinium is
4.07

A
0
, which reveals the molecular stacking eect is very
weak. To our knowledge, the compound is the rst exam-
ple of chlorobismuthate(III) complexes with mixed
organicinorganic cations.
3.1.2. Structure of [8-hydroxyquinolinium]
6
[Bi
2
Cl
10
]
[BiCl
5
(H
2
O)]6H
2
O (2)
The asymmetric unit is constituted by a half dimer of
[Bi
2
Cl
10
]
4
which has the geometry of two octahetra
sharing one edge, a half monomer [BiCl
5
(H
2
O)]
2
, three
8-hydroxyquinoliniums, and three water molecules
(Fig. 4). In the dimer [Bi
2
Cl
10
]
4
two octahedra of [BiCl
6
]
share one edge which is on the 2 axis (Fig. 5). The distances
of BiCl bridge bonds (2.872(2) and 2.9078(12) A

) are
longer than the others of which the longest one is Bi(1)
Cl(6) bond (2.709(2) A

). The signicant interactions of


the cations and the dimers are through Cl(6) at distances
N Cl of 3.180 A

and Cl(3) at a distance O Cl of


3.027 A

. And these interations cause the relatively longer


bond distance of Bi(1)Cl(6). Other possible hydrogen
bond interactions are listed in Table 3.
Bi(2), Cl(9) and O(4) atoms in the monomeric unit
[BiCl
5
(H
2
O)]
2
are all at the 2 axis (Fig. 5). Through sym-
metry operation these three atoms and the other two Cl
atoms (Cl(7) and Cl(8)) form a distorted octahedron. The
distance of BiCl bond on the 2 axis is the shortest
(2.526(3) A

) while the other four BiCl bond lengths are


in a small range from 2.690(2) to 2.709(2) A

. Among the
variously organized halobismuthate anions it is the rst
case that Bi
3+
cation has H
2
O as a ligand though there
has been reported some solvent adducts of chlorobismuth-
ates such as [Li(THF)
4
]
2
[Bi
2
Cl
8
(THF)
2
], [P(Ph)
4
][Bi
2
Cl
10
(C
3
H
6
O)
2
], N(P(Ph)
3
)
2
[BiCl
5
(HOEt)] [1820], and etc.
Since in the experimental section H
2
O was not used as a
solvent, the ligand H
2
O in the unit may come from: the
direct hydrolysis of the [BiCl
6
]
3
, or the substitution of ace-
tone adducts of chlorobismuthates by the small quantity of
H
2
O in the solvent (Scheme 1). This ligation also manifests
an intermediate phase produced while the chlorobismuth-
ates hydrolyze to the BiOCl. The relatively weak interac-
tion between cations and the monomer is through Cl(8)
at a distance of N Cl of 3.498 A

.
Though the hydrogen atoms that attach to Ow(3) atom
can not be exactly located, the relatively short distances of
Cl(2) Ow(3), Cl(7) Ow(3), and O(4) Ow(3) (3.326,
3.407 and 2.864 A

) show there are H bond interactions


between Ow(3) and the two units (Fig. 5). And the distance
between the ligand H
2
O in the monomer and Cl(5) in the
dimer is relatively short (3.698 A

), indicating a weak inter-


Fig. 4. The independent structure of the compound 2.
Fig. 5. The monomeric and dimeric units in compound 2.
Table 3
Selected hydrogen bonding geometry and close contacts [A

,
o
] for compounds 1, 2
DH Cl1 d(DH) d(H A) d(D A) <DHA Symmetry codes
Compound 1
O2-H2A Cl1 0.820 2.274 3.092 174.84 x+1, y, z+1
N2-H2B OW3 0.860 1.857 2.682 160.18 x1, y, z
N1-H2 OW2 1.012 1.713 2.708 166.81
Compound 2
N1-H1A Cl6 0.86 2.36 3.180 158.5
N3-H3A Cl8 0.86 3.05 3.498 114.5 0.5+x, 0.5+y, z
N2-H2B OW3 0.86 2.09 2.932 164.5
N3-H3A OW2 0.86 2.22 2.986 148.6 x+1/2, y+3/2, z
O1-H1B OW1 0.82 1.86 2.615 153.6
O2-H2A Cl3 0.82 2.23 3.027 165.8 x1/2, y+1/2, z
O3-H3C OW2 0.82 1.93 2.736 169.3
O4-H4C OW3 0.8(3) 2.2(3) 2.936 170(28)
Y.-J. Wang, L. Xu / Journal of Molecular Structure 875 (2008) 570576 573
action between the two units. The molecular packing is
determined by the hydrogen bond interactions just dis-
cussed and by strong p interactions with the intermolecular
distances of about 3.2 A

(Fig. 6).
3.2. IR spectra
The IR spectra of both 1 and 2 show at high wavenum-
bers an absorption centered at 3485 cm
1
assignable to
t(OH) of water molecules. The bands at 1634, 1603,
1562, 1419, 1397 cm
1
were associated with the t
s,as
(C@C)
and t
s,as
(C@N) of the pyridine ring. The bands at 1311,
1091 cm
1
are assigned to stretching vibrations of CO,
which also can be observed in the IR spectrum of the Com-
plexes of the type M(8-hydroxyquinoline)
2
X
2
(where
M = Zn, Co; X = Cl, Br) [21]. And the bands at 884,
878, 761 cm
1
are caused by the c(CH) of the 8-hydroxy-
quinolinium, while the bands at 614, 576, 490 cm
1
may be
assigned to d(OH) and c(CH) of the 8-hydroxyquinolini-
um. t(OH) frequency value of water molecules found here
reveals that the lattice water molecules are only weakly
interacting through hydrogen bonding [22], supporting
our structure hypothesis.
The spectra of the two compounds are dierent in the
absorption band in the range 32502650 cm
1
(Fig. 7). In
compound 1, the strong and broad absorption band with
the major peak at 3200 can be assign to the t(OH) of 8-
hydroxyquinolinium as it is shown in the IR spectrum of
the 8-hydroxyquinoline. The middle bands with the peaks
at 2789 and 2671 cm
1
are attributed to the t(NH) of the
NH O. The t(NH) usually lies in the range 3300
3000 cm
1
. As a result of hydrogen bond interactions, the
frequency of t(NH) will be lower [23,24]. And the sizes of
frequency shift imply degrees of the hydrogen bond inter-
actions, i.e. the shorter the hydrogen bond is, the more it
shifts to the lower bands [25]. In compound 1 the strong
NH O bond (2.682 A

) results in the shift of the fre-


quency of t(NH) to the range 27002650 cm
1
. In com-
pound 2 the strong band with the peak at 3154 cm
1
can
be assign to the t(OH) of 8-hydroxyquinolinium or the
t(NH) of the weaker hydrogen bond NH Cl (3.498 A

).
The band at 2700 cm
1
is assign to the t(NH) of the stron-
ger bond NH Cl (3.180 A

). The existence of the absorp-


tions that are assigned to the stretching vibrations of NH
also shows that the 8-hydroxyquinoline molecules have
been protonated. These results are in accord with the single
crystal X-ray analysis.
3.3. UVvis DRIS spectra and Photoluminescence properties
The UVvis DRIS spectra of compound 1 and 2 (Fig. 8)
show transitions attributable to the quinoline and could
safely be assigned taking into account the literature data
[2628]. It is known that the spectrum of 8-hydroxyquino-
line shows three absorption bands, the rst one in the range
of 220250 nm (UU
*
transition), the second at about
270 nm (r
N
p

py
transition from the electron pair of the
Scheme 1. Two possible way of the formation of the monomeric unit
[BiCl
5
(H
2
O)]
2
.
Fig. 6. The molecular packing which is determined by the hydrogen bond
interactions strong p interactions.
Fig. 7. IR of compound 1 (bottom) and compound 2 (top).
574 Y.-J. Wang, L. Xu / Journal of Molecular Structure 875 (2008) 570576
nitrogen atom in the pyridine ring to the LUMO) and the
third in the range of 300320 nm (HOMOLUMO transi-
tion, corresponding to the p
ph
p

py
process). In Fig. 8,
the strong absorption bands with main peaks at 336 nm
(compound 1) and 315 nm (compound 2) are assigned to
the r
N
p

py
transitions of the protonated 8-hydroxyquino-
line, and the absorption bands with peaks at about 406
(1 and 2) are attributable to the p
ph
p

py
transition accord-
ing to the reference [29].
The uorescent spectra of compound 1 and 2 at room
temperature are shown in Fig. 9. On excitation at 314
nm, the sample of 1 gives a strong emission band at
k
max
= 477 nm. And 2 gives a strong emission band at
k
max
= 512 nm on excitation at 300 nm. Comparing the
emission spectra of 1 and 2 with those reported in the liter-
ature for a series of 8-hydroxyquinoline complexes which
show emission peaks at the ranges of 470510 nm and
590630 nm [30]. We think this luminescence probably
may originate from the protonated 8-hydroxyquinoline
ligand. In particular, the 477 nm transition, arising from
an electron charge-transfer from the phenolic to the pyridyl
side of the two-ring fused quinolinol system [31], can be
assigned to an intraligand charge-transfer (ILCT) transi-
tion according to the Vogler notation [32].
4. Conclusions
Two novel chlorobismuthate(III) complexes [8-
hydroxyquinolinium]
4
-K
2
[BiCl
6
]
2
6H
2
O (1) that contains
one-dimensional inorganic zigzag chain and [8-hydroxy-
quinolinium]
6
[Bi
2
Cl
10
][BiCl
5
(H
2
O)]6H
2
O (2) which has
two dierent anionic units have been synthesized and
characterized by single-crystal X-ray diraction. Two
compounds show intense uorescent properties at room
temperature in solid state. It is suggested that the com-
plexes have potential applications in acting as photoac-
tive material. Synthesis of analogical compounds with
other alkali metal cations to replace the K
+
is
underway.
Acknowledgements
This study was based on work supported by the 973
Program (#2006CB932900) and the National Science
Foundation of China (#20473092).
Appendix A. Supplementary data
Crystallographic data of the two compounds in this
paper have been deposited at the Cambridge Crystallo-
graphic Data Center, CCDC-232964 for compound 1 and
CCDC-650254 for compound 2. Copies of the data can
be obtained free of charge on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (Fax: +44 1223
326 033; e-mail: deposit@ccdc.cam.ac.uk). Supplementary
data associated with this article can be found, in the online
version, at doi:10.1016/j.molstruc.2007.06.003.
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