Hybrid salts of binuclear Bi(III) halide complexes with 1,2-bis(pyridinium)ethane cation: Synthesis, structure and luminescent behavior

Article abstract of DOI:10.1016/j.ica.2016.06.010

Reactions between 1,2-bis(pyridinium)ethane bromide ((BPE)Br₂) and [BiCl₆]^3-/[BiBr₆]^3- in HCl or HBr results in isostructural binuclear complexes (BPE)₂[Bi₂X₁₀] (X = Cl (1) and Br (2)) which were characterized by X-ray diffractometry, IR and Raman spectroscopy. Both complexes manifest orange-red luminescence in solid state.

Full text of DOI:10.1016/j.ica.2016.06.010

Accepted Manuscript
Hybrid salts of binuclear Bi(III) halide complexes with 1,2-bis(pyridini-
um)ethane cation: synthesis, structure and luminescent behavior
Sergey A. Adonin, Marianna E. Rakhmanova, Denis G. Samsonenko, Maxim
N. Sokolov, Vladimir P. Fedin
PII:
S0020-1693(16)30320-6
http://dx.doi.org/10.1016/j.ica.2016.06.010
ICA 17101
DOI:
Reference:
Inorganica Chimica Acta
To appear in:
Received Date:
Revised Date:
Accepted Date:
24 February 2016
6 May 2016
4 June 2016
Please cite this article as: S.A. Adonin, M.E. Rakhmanova, D.G. Samsonenko, M.N. Sokolov, V.P. Fedin, Hybrid
salts of binuclear Bi(III) halide complexes with 1,2-bis(pyridinium)ethane cation: synthesis, structure and
luminescent behavior, Inorganica Chimica Acta (2016), doi: http://dx.doi.org/10.1016/j.ica.2016.06.010
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Hybrid salts of binuclear Bi(III) halide complexes with 1,2-bis(pyridinium)ethane cation:
synthesis, structure and luminescent behavior
Sergey A. Adonina,b,* Marianna E. Rakhmanovaa, Denis G. Samsonenkoa,b, Maxim N.
Sokolova,b, and Vladimir P. Fedina,b
aNikolaev Institute of Inorganic Chemistry SB RAS, 630090, Lavrentiev ave. 3, Novosibirsk,
Russia
bNovosibirsk State University, 630090, Pirogova st. 2, Novosibirsk, Russia
*Corresponding author: Dr. S.A. Adonin, E-mail: adonin@niic.nsc.ru
Abstract. Reactions between 1,2-bis(pyridinium)ethane bromide ((BPE)Br2) and [BiCl6]3-
/[BiBr6]3- in HCl or HBr results in isostructural binuclear complexes (BPE)2[Bi2X10] (X = Cl (1)
and Br (2)) which were characterized by X-ray diffractometry, IR and Raman spectroscopy. Both
complexes manifest orange-red luminescence in solid state.
Keywords: bismuth / halide complexes / luminescence / p-block metals / X-ray diffractometry
1. Introduction
One of the prominent features of many late and post-transition metals is their ability to
form polynuclear halide complexes. This trend is especially remarkable in the case of bismuth in
3+ oxidation state: there is a great structural diversity of structural types, including discrete
anions of various nuclearity (1 to 8) and coordination polymers (mostly one-dimensional) [1-9],
as well as heterometallic derivatives. Apart from purely fundamental interest, this class of
compounds demonstrates a number of interesting and promising physical properties such as
ferroelasticity or semiconductivity [10-20], thermochromism [21-23], photochromism [24-28]
etc.
Within the last decades, there appeared a number of studies focused on luminescent
properties of polynuclear Bi(III) halides (polyhalidebismuthates, or PHB), but they remain
relatively sporadic [29-31]. Generally, it can be noted that in the reported cases the major
contribution to the luminescence is provided by the aromatic cations. It was shown that the role
of anionic part is predominantly “structural”: the crystal packing of PHB units may have a great
influence on optical properties [1]. Very recently we have reported solvatochromic effect for
[Bi2X10]2- complexes containing H2(4,4`-bipy) [32] or H2bpe (H2bpe = 4,4-ethylenebipyridinium)
[33] cations; it was shown that the changes in solvate composition may influence the
luminescent behavior, affecting both emission maxima [32] and intensities [33]. Aiming at

further expansion of the PHB-based luminescent complexes and search for new solvatochromic
materials, we have decided to study the PHBs with the BPE cation. From the structural point of
view, this pyridine-based cation is closely related to the 4,4-ethylenebipyridinium; however, it
could be anticipated that the alkylation at nitrogen would affect its ability to form the NH···X
contacts which are usual for the PHBs containing protonated polypyridines [32-35]. In present
paper, we report the synthesis of two new Bi(III) halide complexes – (BPE)2[Bi2X10] (X =
Cl (1), Br (2)), their structures and the studies of their luminescence in solid state.
2. Experimental Section
All reagents, except of the (BPE)Br2, were obtained from commercial sources and
used as purchased. (BPE)Br2 was obtained according to the previously published
procedure [36] by heating Py and 1,2-dibromoethane (2:1 molar ratio) in dry CH3CN for
24 h. Elemental analysis was performed on a Euro NA 3000 Elemental Analyzer (EuroVector).
Synthesis of (BPE)2[Bi2Cl10] (1). 100 mg (0.32 mmol) of BiCl3 were dissolved in
5 ml of 2M HCl. Solution of (BPE)Br2 (110 mg) in 5 ml of 2M HCl was added. White
crystalline precipitate of
1 started to form immediately and the process completed within
6 h. Yield 86%. For C24H28N4Bi2Cl10 calcd, %: C, 25.2; H, 2.5; N, 4.9; found, %: C, 25.4;
H, 2.6; N, 5.1%. IR (4000-400 cm-1 KBr): 3130 w, 3056 m, 3011 w, 2972 w, 1838 w,
,
1726 w, 1631 s, 1580 m, 1491 s, 1457 m, 1306 w, 1215 w, 1193 s, 1052 w, 953 w, 964 w,
775 s, 678 s, 495 m, 450 w.
Synthesis of (BPE)2[Bi2Br10] (2). The procedure was the same as for
1, using BiOBr
instead of BiCl3 and HBr instead of HCl. Precipitation of begins immediately after the
2
mixing and completes within 20-30 minutes. Yield 91%. For C24H28N4Bi2Br10 calcd, %:
C, 18.1, H, 1.8; N, 3.5; found, %; c, 18.2; H, 1.9; N, 3.7. IR (4000-400 cm-1 KBr): 3126
,
w, 3052 m, 2963 w, 1830 w, 1721 w, 1628 s, 1578 m, 1488 s, 1453 m, 1317 w, 1189 s,
1954 w, 947 w, 858 w, 770 m, 674 s, 492 m, 447 w.
X-ray crystallography. Diffraction data for single crystals of compounds 1 and 2 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
[37]. 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-97 (for 2)
and SHELX-2013 (for 1) software packages [38]. 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 1. Selected bond distances and
angles are listed in Tables 2–3. Crystallographic data have been deposited at the Cambridge

Crystallographic Data Centre under the reference numbers CCDC 1455367 and 1455368 for 1
and 2, respectively, and may be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html.
Luminescence studies. Excitation and emission spectra were recorded with a Horiba Jobin
Yvon Fluorolog 3 photoluminescence spectrometer equipped with a 450 W Xe lamp, an
integration sphere, Czerny–Turner double grating (1200 grooves per mm) excitation and
emission monochromators and an FL-1073 PMT detector. Excitation spectra were recorded in
350-570 nm range and corrected for the spectral distribution of the lamp intensity using a
photodiode reference detector. Emission spectra were recorded from 500 to 900 nm and
corrected for the spherical response of the monochromators and the detector using typical
correction spectra provided by the manufacturer. Additionally, the 1st and 2nd harmonic
oscillations of the excitation source were blocked by edge filters.

Table 1. Crystal data and structure refinement for 1 and 2.
Identification code
1
C24H28Bi2Cl10N4
1144.96
2
C24H28Bi2Br10N4
1589.56
Empirical formula
Formula weight
Crystal system
Space group
a, Å
Monoclinic
C2/c
Monoclinic
C2/c
19.0866(3)
9.84714(11)
20.1054(3)
110.2129(16)
3546.06(9)
4
19.7959(7)
9.9395(3)
20.7937(10)
111.314(5)
3811.6(2)
4
b, Å
c, Å
β, deg.
V, Å3
Z
D(calcd), g/cm3
µ, mm−1
2.145
2.770
10.688
19.727
F(000)
2144
2864
Crystal size, mm
0.45 × 0.08 × 0.08
3.45–32.90
0.15 × 0.04 × 0.02
3.40–29.50
θ range for data collection,
deg.
Index ranges
−29 ≤ h ≤ 28, −14 ≤ k ≤ 15,
−29 ≤ l ≤ 29
−26 ≤ h ≤ 22, −13 ≤ k ≤ 13,
−17 ≤ l ≤ 27
Reflections collected /
independent
39346 / 6271
10805 / 4571
Rint
0.0283
5672
0.0464
3262
Reflections with I > 2σ(I)
Goodness-of-fit on F2
1.067
0.905

Final R indices [I > 2σ(I)]
R indices (all data)
R1 = 0.0323, wR2 = 0.0923
R1 = 0.0368, wR2 = 0.0947
R1 = 0.0373, wR2 = 0.0459
R1 = 0.0707, wR2 = 0.0554
Largest diff. peak / hole, e/Å3
−1.108
5.373 /
−1.502
1.556 /

Table 2. Selected bond lengths and angles for 1.
Bond
d, Å
Bond
d, Å
Bi(1)–Cl(1)
2.6044(9)
2.7013(9)
2.6345(9)
ω, deg.
Bi(1)–Cl(4)
2.7025(9)
2.9365(8)
2.9969(8)
ω, deg.
Bi(1)–Cl(2)
Bi(1)–Cl(6)
Bi(1)–Cl(3)
Bi(1)–Cl(5)
Angle
Angle
Cl(1)–Bi(1)–Cl(2)
Cl(1)–Bi(1)–Cl(3)
Cl(1)–Bi(1)–Cl(4)
Cl(1)–Bi(1)–Cl(6)
Cl(1)–Bi(1)–Cl(5)
Cl(2)–Bi(1)–Cl(4)
Cl(2)–Bi(1)–Cl(6)
Cl(2)–Bi(1)–Cl(5)
Cl(3)–Bi(1)–Cl(2)
87.87(3)
94.32(3)
90.55(3)
88.75(3)
172.24(2)
176.41(3)
93.79(2)
88.54(2)
89.23(3)
Cl(3)–Bi(1)–Cl(4)
Cl(3)–Bi(1)–Cl(6)
Cl(3)–Bi(1)–Cl(5)
Cl(4)–Bi(1)–Cl(6)
Cl(4)–Bi(1)–Cl(5)
Cl(6)–Bi(1)–Cl(5)
Bi(1)i–Cl(6)–Bi(1)
Bi(1)i–Cl(5)–Bi(1)
87.68(3)
175.78(3)
92.51(3)
89.40(2)
93.41(2)
84.62(2)
96.66(3)
94.10(3)
−
−
Symmetry transformations used to generate equivalent atoms: i) x + 1, y, z + ½.

Table 3. Selected bond lengths and angles for 2.
Bond
d, Å
Bond
d, Å
Bi(1)–Br(1)
3.0211(7)
3.0803(7)
2.7230(7)
ω, deg.
Bi(1)–Br(4)
2.7462(8)
2.8407(8)
2.8342(8)
ω, deg.
Bi(1)–Br(2)
Bi(1)–Br(5)
Bi(1)–Br(3)
Bi(1)–Br(6)
Angle
Angle
Br(1)–Bi(1)–Br(2)
Br(3)–Bi(1)–Br(2)
Br(3)–Bi(1)–Br(1)
Br(3)–Bi(1)–Br(4)
Br(3)–Bi(1)–Br(5)
Br(3)–Bi(1)–Br(6)
Br(4)–Bi(1)–Br(1)
Br(4)–Bi(1)–Br(2)
Br(4)–Bi(1)–Br(5)
84.361(19)
171.25(2)
88.14(2)
95.38(2)
88.64(2)
90.69(2)
175.66(2)
92.32(2)
89.25(2)
Br(4)–Bi(1)–Br(6)
Br(5)–Bi(1)–Br(1)
Br(5)–Bi(1)–Br(2)
Br(6)–Bi(1)–Br(1)
Br(6)–Bi(1)–Br(5)
Br(6)–Bi(1)–Br(2)
Bi(1)i–Br(1)–Bi(1)
Bi(1)–Br(2)–Bi(1)i
87.89(2)
93.375(18)
87.294(17)
89.534(16)
176.99(3)
93.758(17)
96.87(3)
94.41(3)
−
−
Symmetry transformations used to generate equivalent atoms: i) x + 1, y, z + ½.
Results and discussion
Synthesis of 1 and 2. The major part of PHBs reported to date is synthesized by a
straightforward approach: “cation + source of halide ion + source of Bi(III)” [1]. In some cases,
cation may be prepared in situ (for example, by protonation of corresponding base [32-34] or N-
alkylation of polypyridyl [26-27]). The source of Bi depends on the nature of the solvent: if
synthesis is carried out in a hydrohalic acid as medium, it may be Bi(III)
oxide/ohyhalide/carbonate etc, resulting in [BiX6]3- after dissolution. In general, there is usually
no direct correlation between the initial stoichiometry and the composition of the products.
However, the use of HCl, HBr or HI as a medium, providing also an excess of corresponding
halide anions in solution, commonly results in complexes with higher X/Bi ratio (4 to 5.5) than

organic solvents. In can be noted also that the binuclear halobismuthates, especially [Bi2X9]3- and
[Bi2X10]4-, are the most widespread PHBs appearing in solid state [1]. Therefore, the formation
of [Bi2X10]4- anionic moieties in 1 and 2 was rather expectable.
Structures of 1 and 2. The structure of chloro- (1) and bromobismuthate (2) anions
−
[Bi2X10]4 is similar to those found in related compounds [32-34, 39-43]. Structures 1 and 2 are
isostructural. The asymmetric unit contains one Bi3+ cation. The Bi cation has octahedral
coordination environment provided by six halides (Cl− or Br−). Two cations are interconnected
via two bridging halide ligands (µ-Cl resp. µ-Br) to form binuclear [Bi2(µ-X)2X8]4− (X = Cl and
Br for 1 and 2, respectively) anion (Fig. 1). Bi–Cl(terminal) distances are in range 2.6044(9)–
2.7025(9) Å, and Bi–Cl(bridging) distances range from 2.9365(8) Å to 2.9969(8) Å. Bi–
Br(terminal) distances are in range 2.7230(7)–2.8407(8) Å and Bi–Br(bridging) distances are in
range 3.0211(7) Å and 3.0803(7) Å, following the same trend. The centers of [Bi2(µ-X)2X8]4−
−
−
anions occupy special positions 4e (0, y, ¼; 0, y, ¾; ½, y + ½, ¼; ½, ½ y, ¾), two bridging
halogenide ligands (Cl(5) and Cl(6) in 1, Br(1) and Br(2) in 2) are situated on two-fold rotation
axis. The organic cations occupy general positions. Fig. 2 shows crystal packing in the structure
1. All the discrete constituents in the structures 1 and 2 are interconnected via van der Waals
interactions.

Fig. 1. Structure of cation and anion in 1 (a) and 2 (b). Symmetry transformations used to generate
−
−
equivalent atoms: i) x + 1, y, z + ½.

Fig. 2. Crystal packing in 1 (H atoms are omitted).
Luminescence studies and Raman spectra. The compounds 1 and 2 manifest orange-red
luminescence in the solid state at room temperature, the excitation and emission spectra of are
displayed in Fig. 3. The excitation maximum for both compounds is about 480 nm. Taking into
account these data, the excitation wavelength 480 nm was used for recording of the emission
spectra. The powders of 1 and 2 exhibit orange-red photoluminescence (PL) with a broad
emission with maxima at ca. 590 nm (Fig. 3).
Fig. 3. Excitation and emission spectra of the compounds 1 (black) and 2 (red)

Comparing these data with those reported earlier [32-34], several interesting observations can be
made. As in the previous studies, the luminescence intensity for bromide complexes is generally
lower than for the chloride analogues (this fact was also noted by Mercier et al. [44]). However,
the extent of this difference varies very strongly, depending on the nature of cation: for 1 and 2, it
is comparable with (H2bpe)2[Bi2Cl10] and (H2bpe)2[Bi2Br10] (H2bpe = 4,4`-ethylenepyridinium)
[33], but it is not so dramatic as in the (H2bpen)2[Bi2X10] (X = Cl, Br) (H2bpe = 4,4`-
vinylenepyridinium) pair [34] or (H2(4,4`-bipy))2[Bi2Br10] [45], where the luminescence of
bromide complex is very weak.
The Raman spectra (see SI) of 1 and 2 are similar to those reported earlier for the other
halobismuthate [46] and other p-block metal halide complexes [47-48]: the 150-310 cm-1 area is
responsible for Bi-X stretching vibrations.
4. Conclusions
To conclude, two new complexes based on 1,2-bis(pyridinium) cations and binuclear [Bi2X10]4-
anions have been presented. Both complexes are luminescent, and the difference between the
chloride (1) and bromide (2) complexes is less pronounced than in some previous examples; this
fact may be of interest for further theoretical studies.
Acknowledgements. This work has been supported by Russian Scientific Foundation (Grant No.
14-23-00013).
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Two organic-inorganic hybrids based on Bi(III) halide complexes; (BPE)2[Bi2X10] (X = Cl, Br) (BPE = 1,2-
bis(pyridinium)ethane) have been prepared. Both complexes display orange–red luminescence; its
intensity is higher for chloride complex than for bromide

-Two hybrid binuclear complexes (BPE)2[Bi2X10] (X = Cl, Br) were synthesized
-Luminescent behavior was studied