Halobismuthates with bis(pyridinium)alkane cations: Correlations in crystal structures and optical properties

Article abstract of DOI:10.1016/j.ica.2017.08.058

A series of four chloro- and bromobismuthates with bis(pyridinium)alkane cations (Py(CH₂)_nPy)²⁺(C_n) and (4-PyH)(CH₂)_n(4-PyH)²⁺(H₂C_n) were synthesized and characterized. Analysis of their crystal structures, as well as previously reported data, results in establishment of correlations between the type of halobismuthate anion and the nature of cation. Luminescent properties of obtained compounds are reported and discussed.

Full text of DOI:10.1016/j.ica.2017.08.058

Accepted Manuscript
Research paper
Halobismuthates with bis(pyridinium)alkane cations: correlations in crystal
structures and optical properties
Sergey A. Adonin, Igor D. Gorokh, Denis G. Samsonenko, Olga V. Antonova,
Ilya V. Korolkov, Maxim N. Sokolov, Vladimir P. Fedin
PII:
S0020-1693(17)30770-3
http://dx.doi.org/10.1016/j.ica.2017.08.058
ICA 17852
DOI:
Reference:
Inorganica Chimica Acta
To appear in:
Received Date:
Revised Date:
Accepted Date:
16 May 2017
19 July 2017
25 August 2017
Please cite this article as: S.A. Adonin, I.D. Gorokh, D.G. Samsonenko, O.V. Antonova, I.V. Korolkov, M.N.
Sokolov, V.P. Fedin, Halobismuthates with bis(pyridinium)alkane cations: correlations in crystal structures and
optical properties, Inorganica Chimica Acta (2017), doi: http://dx.doi.org/10.1016/j.ica.2017.08.058
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Halobismuthates with bis(pyridinium)alkane cations: correlations in
crystal structures and optical properties
Sergey A. Adonin,*a,b Igor D. Gorokh,b Denis G. Samsonenko,a,b Olga V. Antonova,a Ilya V. Korolkov,a,b
Maxim N. Sokolova,b,c and Vladimir P. Fedina,b
a) Nikolaev Institute of Inorganic Chemistry SB RAS, 630090 Lavrentieva St. 3, Novosibirsk, Russia. E-
mail: adonin@niic.nsc.ru
b) Novosibirsk State University, 630090 Pirogova St.2, Novosibirsk, Russia
c) Kazan Federal University, Alexander Butlerov Institute of Chemistry, Lobachevskogo str. 1/29,
420008 Kazan, Russia
Abstract: A series of four chloro- and bromobismuthates with bis(pyridinium)alkane cations
(Py(CH2)nPy)2+ (Cn) and (4-PyH)(CH2)n(4-PyH)2+ (H2Cn) were synthesized and characterized. Analysis of
their crystal structures, as well as previously reported data, results in establishment of correlations
between the type of halobismuthate anion and the nature of cation. Luminescent properties of
obtained compounds are reported and discussed.
Keywords: halometalate / halide complexes / bismuth / luminescence / crystal structure
Introduction
Halide complexes of late transition and post-transition metals (in particular, bismuth) evoke a
significant interest due to a number of promising physical properties,1,2 including
ferroelectricity
and
ferroelasticity,3-9
thermochromism,10,11
luminescence,12-15
photochromism16-19 and photocatalytic activity.20-24 From the point of view of coordination
chemistry, an attractive feature of this class of compounds is their remarkable structural
diversity.1-2 Due to the oligomerization via bridging halide ligands, halobismuthates can reach
nuclearity of up to 8 Bi (for discrete anions),24-33 as well as form various, predominantly 1D,
polymers25,34-36 and heterometallic complexes.37-39 However, synthesis of such complexes
cannot be always controlled in a straightforward, i.a. stoichiometric, way: even when well
defined amounts of all reagents are used, the final X/metal ratio and the structure of forming
halobismuthate will vary and cannot be precisely predicted. It was noted2, 40 that one of the

key factors in these processes is the nature (geometry and charge) of cationic part, but the
exact correlations are still to be found. The same observations were made also for other
metal halide complexes.20-23 Therefore, information on new halobismuthates, especially
within the families of related cations, is needed. The importance of such studies becomes
especially evident considering the increasing interest in the iodometalate systems which are
widely used in the “perovskite-type” solar cells.
In this work, we present a set of new compounds containing bis(pyridinium)alkane cations
with a different number of CH2 groups between the pyridine rings (Cn) or bis-protonated 1,X-
bis(4-pyridinium)alkanes (H2Cn). These are (C3)3[Bi2Cl9]2 (
1), (H2C3)2[Bi2Cl10] (2), (C4)3[BiBr6]2 (3)
and (C5)3[Bi2Br9]2 (4). All compounds are luminescent (QY up to 5.08%). Tentative correlations
between the type of cation and the structure and stoichiometry of the anion, based both on
new and previously reported data are discussed, as well as the comparison of optical
properties.
Experimental section
General
All chemicals and solvents were of reagent grade. Elemental analysis was performed on a
Euro NA 3000 Elemental Analyzer (EuroVector). Bis(pyridinium)propane, butane and pentane
dibromide salts (C3Br2, C4Br2 and C5Br2) were obtained by reactions of 2 equivalents of
pyridine and 1.15 equivalent of corresponding dibromoalkane in acetonitrile (reflux, 24 h) and
identified by 1H NMR spectra (yield > 90%, see SI for details).
Synthetic procedures
Synthesis of (C3)3[Bi2Cl9]2 (1)
130 mg (0,280 mmol) Bi2O3 were dissolved in 6 ml of 2 M HCl (solution 1). Separately, 1,3-
(N,N’)-bispyridylpropane bromide (C3Br2) (200 mg, 0,559 mmol) was dissolved in distilled
water (7 ml) and silver nitrate (200 mg, 1,176 mmol) was added with strirring. After 30 min,
precipitate of AgBr was filtered off, and 1.5 ml of 12M HCl added and resulting solution was
added to solution 1. White crystalline precipitate starts to form; the process complexes after
2-3 hours when cooled (6°C). Single crystals suitable for X-ray diffraction were isolated from
the precipitate. Yield 78%. For C39H48N6Bi4Cl18 calcd, %: C, 22.7; H, 2.3; N, 4.1; found, %: C,
22.8; H, 2.5; N, 4.2.

Synthesis of (H2C3)2[Bi2Cl10] (2)
BiCl3 (200 mg, 0.634 mmol) was dissolved in 6 ml of 5M HCl. Solution of 4,4’-
trimethylenedipyridine (bpp) (125 mg, 0.631 mmol) in 5 M HCl (5 ml) was added. Within 1 h,
2
precipitates in form of colorless crystals suitable for XRD. Yield 91%. For C26H32N4Bi2Cl10 calcd,
%: C, 26.7; H, 2.8; N, 4.8; found, %: C, 26.6; H, 2.9; N, 5.0.
Synthesis of (C4)3[BiBr6]2 (3)
Solid BiOBr (27 mg, 0,089 mmol) was dissolved in 2 M HBr (5 ml). A solution of 1,4-(N,N’)-
bispyridylbutane bromide (50 mg, 0,134 mmol) in 2 M HBr (5 ml) was added. Light yellow
crystalline precipitate was formed during next hour. Single crystals suitable for X-ray
diffraction were isolated from the precipitate. Yield 87%. For C42H54N6Bi2Br2 calcd, %: C, 25.1;
H, 2.7; N, 4.2; found, %: C, 25.0; H, 2.8; N, 4.3.
Synthesis of (C5)3[Bi2Br9]2 (4)
The procedure is very similar to
1
, except of using C5Br2 as is and HBr except of HCl. Pale
. Yield 84%. For C45H60N6Bi4Br18 calcd, %:
yellow crystals of 4 form more rapidly than those of
1
C, 18.4; H, 2.1; N, 2.9; found, %: C, 18.2; H, 2.1; N, 3.1.
X-ray diffractometry
Diffraction data for single crystals of compounds 1–4 were obtained at 130 K on an
automated Agilent Xcalibur diffractometer equipped with a CCD AtlasS2 detector (MoKα,
graphite monochromator, ω-scans). Integration, absorption correction, and determination of
unit cell parameters were performed using the CrysAlisPro program package. The structures
were solved by a direct method and refined by the full-matrix least squares technique in the
anisotropic approximation (except hydrogen atoms) using the SHELX-2014 software
package.43 Positions of hydrogen atoms of organic ligands were calculated geometrically and
refined in the riding model. The crystallographic data and details of the structure refinements
are summarized in Table 2. Selected bond distances and angles are listed in Tables S1–S4 (see
SI). CCDC 1536840-1536843 contain the supplementary crystallallographic data for
compounds
1
-4
.
These
data
can
be
obtained
free
of
charge
via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or e-mail: deposit@ccdc.cam.ac.uk.

Table 1. Crystal data and structure refinement.
Complex
Empirical
formula
1
C39H48Bi4Cl18N6
2
C26H32Bi2Cl10N4
3
C42H54Bi2Br12N6
4
C45H60Bi4Br18N6
M, g/mol
2074.85
130
1173.01
130
2019.79
130
2959.29
130
Temperature, K
Crystal system
Space group
a, Å
Monoclinic
P21/n
Triclinic
P−1
Monoclinic
Pc
Monoclinic
P21
17.2682(3)
10.1059(2)
36.1715(7)
90
8.8918(2)
9.1213(2)
11.6352(3)
87.395(2)
83.901(2)
73.341(2)
898.84(4)
1
12.2232(3)
10.6810(2)
21.6436(5)
90
15.1108(3)
11.1199(2)
21.7559(4)
90
b, Å
c, Å
α, deg.
β, deg.
γ, deg.
V, Å3
101.764(2)
90
93.734(2)
90
95.9225(19)
90
6179.7(2)
4
2.230
2819.70(11)
2
2.379
3636.14(12)
2
2.703
Z
D(calcd), g/cm3
2.167
μ, mm−1
F(000)
12.169
3848
10.544
552
14.770
1868
Crystal size, mm 0.26 × 0.19 × 0.14 0.41 × 0.25 × 0.23 0.40 × 0.24 × 0.13
19.574
2668
0.33 × 0.08 × 0.06
3.27–25.68
θ range for data
collection, deg.
Index ranges
3.28–25.35
3.48–29.46
3.34–29.07
−20 ≤ h ≤ 20,
−10 ≤ k ≤ 12,
−36 ≤ l ≤ 43
−10 ≤ h ≤ 11,
−8 ≤ k ≤ 11,
−15 ≤ l ≤ 13
6854 / 4121
−12 ≤ h ≤ 16,
−14 ≤ k ≤ 13,
−29 ≤ l ≤ 27
15353 / 8741
−15 ≤ h ≤ 18,
−12 ≤ k ≤ 13,
−24 ≤ l ≤ 26
Reflections
collected /
independent
Rint
30129 / 11251
18745 / 11685
0.0241
10106
0.0429
3785
0.0281
8475
0.0281
10756
Reflections with
I > 2σ(I)
Goodness-of-fit
on F2
1.064
1.002
1.049
0.974
Final R indices
[I > 2σ(I)]
R1 = 0.0257, wR2 =
0.0538
R1 = 0.0297,
wR2 = 0.0572
R1 = 0.0337,
wR2 = 0.0589
R1 = 0.0250, wR2 =
0.0531
R1 = 0.0327, wR2 =
0.0623
R indices (all
data)
R1 = 0.0314, wR2 =
0.0558
−1.163
2.740 /
R1 = 0.0265, wR2 =
0.0538
R1 = 0.0376, wR2 =
0.0648
−2.321
−
2.043 / 2.156
−1.671
1.787 /
Largest diff.
peak / hole,
e/Å3
1.439 /
Luminescence studies
Room temperature excitation and emission spectra were recorded with a Horiba Jobin Yvon
Fluorolog 3 photoluminescence spectrometer equipped with a 450 W ozone-free Xe lamp, an
integration sphere, double grating excitation and emission monochromators. Emission and

excitation spectra were corrected for source intensity (lamp and grating) and emission
spectral response (detector and grating) by standard correction curves.
Results and discussion
As it was mentioned by us earlier,40 synthesis of halobismuthates using hydrohalic acid as
solvent and a source of halide ligands usually results in complexes with relatively high X/Bi
ratio. However, although it can be expected that the formation of the most-halide-saturated
species (in respect to the mononuclear [BiX6]3- as the limit) must be favorable, it occurs only in
few cases; the most common products are [Bi2X9]3-, [Bi2X10]4- and polymeric [{BiX4}n]n- or
[{BiX5}n]2n- of different structural types.40 It has been suggested that the key factor driving the
self-assembly towards a specific anion is the nature of cation (its geometry and charge
distribution).
Comparing our results with the halobismuthates reported earlier,40 we could note several
interesting correlations. According to the Cambridge Structural Database, there are 54
complexes containing [Bi2X10]4- anion and characterized by XRD (excluding duplicated data). In
48 cases (89%), the cations are protonated N-bases or H3O+, sometimes (21 structures or
39%) accompanied by solvate H2O molecules. The statistics for the [Bi2X9]3- – containing
complexes is dramatically different: there are also 54 (!) compounds, but only 14 of them
(26%) contain protonated cations. As it is cited in the relevant articles, the presence of
specific EH···X interactions is very common for [Bi2X10]4- halobismuthates; hence we can
propose that it is the ability of a cation to build such contacts that is responsible for the
favorable formation of anions of this type. And the new complexes, except for
3
, clearly
ꢀ ꢀ
[Bi2X10]4- N-alkylated C3 and C5 [Bi2X9]3-,
,
match this principle (protonated base H2C3
respectively).
The structures of the haloantimonates are usually similar to halobismuthates, although not all
types or anions were encountered for both metals. However, the known structures obey the
same principle: in all 9 cases, crystallization of [Sb2X10]4- occurs in the presence of protonated
amines.
Another observation can be made when analyzing the crystal systems the halobismuthates of
various types crystallize in. For [Bi2X10]4-, the most common crystal systems tend to lower
symmetry: triclinic (35,2%, 19 cases) and monoclinic (59,3%, 32 cases); there are only three
(5,5%) complexes crystallizing in orthorhombic space groups. For [Bi2X9]3-, the distribution is

more diverse (including tetragonal and hexagonal space groups); the situation is quite similar
for related haloantimonates, although their overall number is lower (See Table 1).
Table 1. Distribution of crystal structures of [M2X10]4- and [M2X9]3- halometalates (M = Sb, Bi)
among the crystal systems
Anion
Triclinic
Monoclinic Orthormobic Tetragonal Hexagonal
Total
n
19
9
%
n
%
n
3
%
6
n
0
1
1
0
1
%
0
n
0
9
0
9
0
%
0
{Bi2X10}
{Bi2X9}
35
17
56
8
32
25
2
59
46
22
38
54
54
54
9
10
1
18
11
19
6
2
17
0
{Sb2X10}
5
11
0
{Sb2X9}
All
2
10
34
5
35
0
26
63
24
38
4
2
{M2X10}
All
11
14
35
44
15
19
1
1
18
22
80
{M2X9}
Complexes 1, 2 and
4 crystallize in the space groups P21/n, P−1 and P21, respectively,
belonging therefore to the monoclinic and triclinic crystal systems, which are, as mentioned
above, common for the halobismuthates of corresponding structural types. Obviously, in
some cases possible correlations between the point group of anion and overall crystal
symmetry may exist. Similar observations can be made when analyzing the statistics on the
bromo- and iodoplumbates, in particular with a series of closely related cations and
synthesized under intentionally standardized conditions.41
Our efforts to isolate the bromobismuthate analog of
1 using the same synthetic strategy
were not successful. Although precipitation does occur and numerous attempts were
undertaken, they always resulted in powders containing very small crystals of low quality.
According to PXRD data, it is not isostructural to 1, although elemental analysis data gave the
ratio close to the calculated for a [Bi2Br9]3-salt.
The anionic parts of
with a shared face. The bong lengths fit within the ranges usual for this type:40 the Bi-Xterm are
2.54-2.58 and 2.69-2.74Å, respectively. The Bi-μ2-X are longer: 2.83-2.93 in and 2.95-3.11 Å
1 and 4
consist of binuclear [Bi2X9]3- anions built of two {BiX6} octahedra
1

in 4; in the latter case, the length of the shortest Bi-Br bond (2.949(2)Å) is slightly less than
that found in related complexes (2.98-3.10Å).40 In both cases, there may be found CH···X
contacts between the cations and [Bi2X9]3- anions. When limiting the length of H···Cl
interactions to 2.85 Å, there are three sorts of C3 cations engaged into 5, 6 and 7 contacts and
connecting 3, 4 and 4 [Bi2Cl9]3- units, respectively (Fig. 1). The shortest CH···Cl distances are
2.559(1) Å, corresponding to the contact between 2H atom on one of the Py rings and a μ2-Cl
ligand; the rest is noticeably longer. The crystal packing in 1 is shown in Fig. 2.
Figure 1. C-H···Cl interactions (dashed) in the crystal structure of 1. [Bi2Cl9]3- anions are shown as
polyhedra, H atoms not involved in cation-anion interactions are omitted for clarity
The system of cation-anion interactions, as well as crystal packing in
sophisticated. The C-H···Br contacts are expectedly longer than C-H···Cl in
4
(Fig. 3) is more
1
. Interestingly, the
shortest distances (2.728(2) Å) correspond also to the C-H-μ2Br contacts, i.e., to the bromide
ligands with the longest Bi-Br bonds; while the minimal C-H···Brterm distances are 2.835(2) Å.

Figure 2. Crystal packing in the structure of 1 polyhedra, H atoms not involved in cation-anion
interactions are omitted for clarity
Figure 3. Crystal packing in the structure of 4

In the case of 2
, the shortest contacts between the H2C3 and [Bi2Cl10]4- units are NH···Cl. Each
H2C3 cation is connected with one μ2-Cl (2.423(1) Å) and one terminal chloride ligand
(2.504(1) Å). All CH···Cl distances are longer (≈ 2.6 Å), being therefore comparable with those
found in 1. These facts are in a very good agreement with the observations mentioned above:
the presence for N-protonated cations results in short NH···X contacts, making the formation
of [Bi2X10]4- type anion favourable.
Figure 4. NH···Cl interactions (dashed) in the crystal structure of 2
The statistics on the mononuclear [BiX6]3- complexes seems to be less informative. There is a
great variety of possible symmetries: crystallization in triclinic or monoclinic crystal systems is
not uncommon, but there are also numerous examples of hexagonal, tetragonal and
orthorhombic structures without any clear favourability. The cations may be also different,
but almost in all cases their nature enables the formation of short EH···X contacts (N-
protonated bases, NH2 substituents, aqua ligands in the coordination spheres of complex
cations etc). From this point of view, the structure of
extraordinary example. The shortest CH···Br interactions (≈ 2.7 Å) are comparable with those
found in
3 (Fig. 5) may be considered as an
4.

Figure 5. Crystal packing in the structure of 3
Photoluminescence excitation and emission spectra of chlorobismuthates
1 and 2 are
displayed in Fig. 6. In the case of 1, at λex=440nm there is emission maximum with λmax
530nm (broad structureless band). The spectrum of (λex = 450nm) has two bands: a low-
intensity band with the maximum at λmax=530nm and a high intensity band with the
=
2
maximum at λmax=700nm. The fluorescence quantum yields of
5.08% and 2.06%, respectively.
1 and 2 were determined to be
Figure 6. Normalized excitation spectra of 1 (a) and 2 (b); normalized luminescence spectra of 1 with
excitation an 440 nm (c) and 2 at 450 nm (d)

Photoluminescence excitation and emission spectra of
3
and
4
are given on Fig. 7. For both
and . This fact
compounds, quantum yields are significantly lower (less than 0.2%) than for
1
2
agrees with the observations made earlier: intensity and (sometimes) quantum yields are
generally lower for bromobismuthates than for chlorobismuthates;13 in some cases, there is
no detectable emission at room temperature, and it can be detected only when cooling.42
emits in the blue-green part of the spectrum (λex=360 nm) with the maximum at λmax=440nm.
In the case of , there is a broad structureless band with λmax=600 nm (λex=530 nm).
3
4
Figure 7. Normalized excitation spectra of 3 (a) and 4 (b); normalized luminescence spectra of 3 with
excitation at 360 nm (c) and of 4 with excitation at 530 nm (d)
For all precursors, measurements of luminescence in solid state have been carried out as well (see
SI). Based on these data, we could conclude that the appearance of luminescence properties for 1-4
is due to the presence of corresponding organic cations; the amplification of emission intensity may
be due to the packing effects (see SI).
Considering the fact that 3 and 4 crystallize in acentric polar space groups, it can be expected that
these complexes may also reveal non-linear optical properties as well as piezoelectric properties.
Such behavior was earlier reported for other halometalates.44-46
Conclusions

Four new bromo- and chlorobismuthate complexes were synthesized and structurally
characterized. There are some general trends in the distribution of a large number of
previously reported halobismuthates as well as new structures of 1-4 among the structural
types. First, the presence of N-protonated bases (i.e. amines) and/or other fragments
enabling the formation of shorter (2.4-2.55 Å for X = Cl) cation-anion EH···X contacts (such as
hydroxo or amino groups in organic ligands in a complex cation) promotes the formation of
[Bi2X10]4- and, rather often, even [BiX6]3- anions. Second, if the nature of cation does not make
the appearance of such interactions favourable, there usually form [Bi2X9]3- anions. In these
cases, there may be found CH···X contacts, but they are always longer (usually by 0.1-0.15 Å).
Third, the shortest EH···X distances are observed for bridging halide ligands (in other words,
the longer is Bi-X, the shorter is EH···X). Similar observations can be made for isostructural
haloantimonates. Although the scope of these observations does not cover all halometalate
(and even halobismuthate) types, we hope that it may be applied in further structural
analysis, aiming at the development of crystal engineering of halometalates with desired
physical properties.
Acknowledgements
This work has been supported by Russian Science Foundation (Grant No. 14-23-00013). S.A.
Adonin thanks the President of Russia for research fellowship. The authors thank one of the
referees for valuable suggestions.
Supplementary Information
Details of PXRD experiments, PXRD data for 1-4, selected bond lengths for 1-4, description of
synthetic procedures for precursors, luminescence spectra of precursors.
References
1 L.-M. Wu, X.-T. Wu, L. Chen, Coord. Chem. Rev. 2012, 253, 2787
2 N. Mercier, N. Louvain, W.H. Bi, CrystEngComm 2009, 11, 720
3 B. Kulicka, T. Lis, V. Kinzhybalo, R. Jakubas, A. Piecha, Polyhedron 2010, 29, 2014
4 J. Przesławski, A. Piecha-Bisiorek, R. Jakubas, J. Mol. Struct. 2016, 1110, 97
5 M. Chański, A. Białonska, R. Jakubas, A. Piecha-Bisiorek, Polyhedron 2014, 71, 69
6 M. Owczarek, R. Jakubas, A. Pietraszko, W. Medycki, J. Baran, Dalton Trans. 2013, 42, 15069

7 J. Przeslawski, W. Medycki, A. Piecha, R. Jakubas, D. Kruk, Chem. Phys. 2013, 410, 19
8 I. Płowaś, G. Bator, R. Jakubas, J. Baran, Vibr. Spectosc. 2012, 62, 121
9 I. Płowaś, B. Białońska, G. Bator, R. Jakubas, W. Medycki, J. Baran, Eur. J. Inorg. Chem. 2012,
636
4
,
10A. Gagor, M. Wecławik, B. Bondzior, R. Jakubas, CrystEngComm 2015, 27, 3286
11M.A. Tershansy, A.M. Goforth, J.R. Gardinier, M.D. Smith, L. Peterson, H.C. zur Loye, Solid
State Sci. 2007, , 410
9
12Y.-J. Wang, L. Xu, J. Mol. Struct. 2008, 875, 570
13O. Toma, N. Mercier, C. Botta, Eur. J. Inorg. Chem. 2013, 1113
14A.W. Kelly. A. Nicholas, J.C. Ahern, B. Chan, H.H. Patterson, R.D. Pike, J. Alloys Compd. 2016,
670, 337
15A.S. Rao, E.S. Babu, K.C.K. Swamy, S.K. Das, Polyhedron 2010, 29, 1706
16N. Leblanc, M. Allain, N. Mercier, L. Sanguinet, Cryst. Growth Des. 2011, 11, 2064
17R.G. Lin, G. Xu, M.S. Wang, G. Lu, P.X. Li, G.C. Guo, Inorg. Chem. 2013, 52, 1199
18R.G Lin, G. Xu, G. Lu, M.S. Wang, P.X. Li, G.C. Guo, Inorg. Chem. 2014, 53, 5538
19T.-L. Yu, P.-F. Hao, J.-J. Shen, H.-H. Li, Y.-L. Fu et al. Dalton Trans. 2016, 45, 16505
20X.-W. Lei, C.-Y. Yue, J.-Q. Zhao, Y.-F. Han, J.-T. Yang, R.-R. Meng, C.-S. Gao, H. Ding, C.-Y. Wang,
W.-D. Chen. Cryst. Growth Des. 2015, 15, 5416.
21X.-W. Lei, C.-Y. Yue, L.-J. Feng, Y.-F. Han, R.-R. Meng, J.-T. Yang, H. Ding, C.-S. Gao, C.-Y. Wang.
CrystEngComm 2016, 18, 427
22X.-W. Lei, C.-Y. Yue, J.-Q. Zhao, Y.-F. Han, J.-T. Yang, R.-R. Meng, C.-S. Gao, H. Ding, C.-Y. Wang,
W.-D. Chen, M.-C. Hong. Inorg. Chem. 2015, 54, 10593.
23X.-W. Lei, C.-Y. Yue, J.-C. Wei, R.-Q. Li, Y. Li, F.-Q. Mi. Dalton Trans. 2016, 45, 19389.
24V.V. Sharutin, I.V. Egorova, N.N. Klepikov, E.A. Boyarskaya, O.K. Sharutina, Russ. J. Inorg.
Chem. 2009, 54, 1768
25H. Krautscheid, Z. Anorg. Allg. Chem. 1995, 621, 2049
26C. Feldmann, J. Solid State Chem. 2003, 172, 53
27B.G. Chen, J. Clust. Sci. 2017, 28, 983
28C.J .Carmalt, W. Clegg, M.R. J. Elsegood, R.J. Errington, J. Havelock, P. Lightfoot, N.C. Norman,
A.J. Scott, Inorg .Chem. 1996, 35, 3709
29V.Y. Kotov, A.B. Ilyukhin, A.A. Sadovnikov, K.P. Birin, N.P. Simonenko, H.T. Nguyen, A.E.
Baranchikov, S.A. Kozyukhin, Mendeleev Commun. 2017, 27, 271
30G.A. Bowmaker, P.C. Junk, A.M. Lee, B.W. Skelton, A.H. White, Austr. J. Chem. 1998, 51, 293

31V.Y. Kotov, A.B. Ilyukhin, K.P. Birin, V.K. Laurinavichyute, A.A. Sadovnikov, Z.V. Dobrokhotova,
S.A. Kozyukhin, New J. Chem. 2016, 40, 10041
32G.A. Bowmaker, F.M.M. Hannaway, P.C. Junk, A.M. Lee, B.W. Skelton, A.H. White, Austr. J.
Chem. 1998, 51, 325
33G.A. Bowmaker, F.M.M. Hannaway, P.C. Junk, A.M. Lee, B.W. Skelton, A.H. White, Austr. J.
Chem. 1998, 51, 331
34O. Toma, N. Mercier, M. Allain, C. Botta, CrystEngComm 2013, 15, 8565
35D.B. Mitzi, P. Brock, Inorg. Chem. 2001, 40, 2096
36Z.Y. Chen, S. Lin, Y.L. Huang, B.G. Chen, J. Clust. Sci. 2017, 28, 1551
37C. Feldmann, Inorg .Chem. 2001, 40, 818
38W.X. Chai, L.M. Wu, J.Q. Li, L. Chen, Inorg. Chem. 2007, 26, 1042
39M.-W. Yan, L.-H. Li, L. Chen, Z. Anorg. Allg. Chem. 2009, 635, 1645
40S.A. Adonin, M.N. Sokolov, V.P. Fedin, Coord. Chem. Rev. 2016, 312, 1
41V. Gomez, O. Fuhr, M. Ruben, CrystEngComm 2016, 18, 8207
42S.A. Adonin, M.N. Sokolov, M.E. Rakhmanova, A.I. Smolentsev, D.P. Pishchur, I.V. Korolkov,
S.G. Kozlova, V.P Fedin, J. Mol. Struct. 2016, 1112, 21
43. G.M. Sheldrick, Acta Cryst. C 2015, C71, 3
44. M. Owczarek, P. Szklarz, R. Jakubas, A. Miniewicz, Dalton Trans. 2012, 41, 7285
45. H. Ratajczak, S. Debrus, R. Jakubas, J. Baran, Bull. Pol. Ac.: Chem. 2000, 48, 193
46. A. Piecha, R. Jakubas, G. Bator, J. Baran, Vibr. Spectrosc. 2009, 51, 226

-A series of hybrid complexes (cation)2[Bi2X10], (cation)3[Bi2X9]2 and (cation)3[BiX6]2 (X = Cl, Br) were
synthesized
-possible correlations between the nature of cation and forming anion are proposed
-Luminescent behavior was studied