A Novel Family of Polyiodo-Bromoantimonate(III) Complexes: Cation-Driven Self-Assembly of Photoconductive Metal-Polyhalide Frameworks

Article abstract of DOI:10.1002/chem.201802100

In the presence of different cations, reactions of [SbBr₆]^3? and I₂ result in a new family of diverse supramolecular 1D polyiodide-bromoantimonate networks. The coordination number of Sb, as well as geometry of assembling {I_x}^n? polyhalide units, can vary, resulting in unprecedented structural types. The nature of I???Br interactions was studied by DFT calculations; estimated energy values are 1.6–6.9 kcal mol^?1. Some of the compounds showed strong photoconductivity in thin films, suggesting multiple feasible applications in optoelectronics and solar energy conversion.

Full text of DOI:10.1002/chem.201802100

A Journal of
Accepted Article
Title: A novel family of polyiodo-bromoantimonate(III) complexes:
cation-driven self-assembly of photoconductive metal-polyhalide
frameworks
Authors: Sergey A. Adonin, Liubov Udalova, Pavel Abramov,
Alexander Novikov, Irina Yushina, Ilya Korolkov, Evgeniy
Semitut, Tatiyana Derzhavskaya, Keith Stevenson, Pavel
Troshin, Maxim Sokolov, and Vladimir Fedin
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To be cited as: Chem. Eur. J. 10.1002/chem.201802100
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10.1002/chem.201802100
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A novel family of polyiodo-bromoantimonate(III) complexes:
cation-driven self-assembly of photoconductive metal-polyhalide
frameworks
Sergey A. Adonin,*[a] [b] Liubov I. Udalova,[a] [b] Pavel A. Abramov,[a] [b] Alexander S. Novikov,[c] Irina V.
Yushina,[a] Ilya V. Korolkov,[a] [b] Evgeniy Yu. Semitut,[a] Tatiyana A. Derzhavskaya,[d] Keith J.
Stevenson,[e] Pavel A. Troshin,[d] [e] Maxim N. Sokolov[a] [b] and Vladimir P. Fedin[a] [b]
Abstract: In presence of different cations, reactions of [SbBr6]3- and
I2 result in a new family of diverse supramolecular 1D polyiodide-
bromoantimonate networks. Coordination number of Sb, as well as
geometry of assembling {Ix}n- polyhalide units, can vary, resulting in
unprecedented structural types. The nature of I···Br interactions was
studied by DFT calculations; estimated energy values are 1.6–6.9
kcal/mol. Some of the compounds showed strong photoconductivity
in thin films, suggesting multiple feasible applications in
optoelectronics and solar energy conversion.
polyhalides ((BrI2)-, (ClBr2)-) was reported mostly for heteroligand
complexes.18-21
Very recently, we discovered a series of Bi(III) polybromide
complexes, featuring a remarkable structural diversity and
containing {Brx} units of variable nuclearity (up to 9).22 In all
cases, the compounds were obtained by a straightforward
method: “[BiBr6]3- + Br2 + (cation)Brx + HBr”. Geometry of the
cation plays crucial role, promoting formation of a particular type
of 0D, 1D or 2D-anion. Analyzing the earlier publications, we
noticed that the studies of corresponding reactions with [SbBr6]3-
were performed by Lawton et al. decades ago. The authors
found that these reactions are also cation-dependent, but the
nature of possible products may be here even more diverse due
to the ability of Sb (III) to be oxidized by Br2 into [SbBr6]-.23-25
Therefore, there appear six possible combinations: Sb(III), Sb(V)
or mixed-valent complex with or without polybromide units in the
structure. Although these results are very inspiring and
interesting from the point of view of chemistry of both p-block
metals and halogens, and this work can be expanded, we could
not find consequent studies in this field. Attempting to fill this gap,
we decided to investigate behavior of bromoantimonate (III)/HBr
systems in presence of I2 assuming that: 1) Sb(III) cannot be
oxidized into Sb(V) by I2, 2) mixed bromide/polyiodide
complexes may form, which, considering the enhanced ability of
iodine to build extended polyhalide units, might attain higher
dimensionality, and 3) these compounds might display narrow
optical band gaps, which are attractive for designing
iodometalate-based solar cells.26-29
Introduction
Although the first polyhalides were discovered decades ago, this
field of chemistry has been progressing, resulting in an
astonishing variety of compounds, often with promising
properties,1-3 and it keeps providing the chemical community
with unexpected and fascinating results. The most recent
advances were achieved in the area of non-iodide polyhalides,
for example, synthesis and theoretical studies of enhanced
polybromide frameworks4-6 and polychlorides;7 the latter are of
special interest due to the clearly decreasing ability to form
polyhalides in the I > Br > Cl >> F row. However, despite the
general progress in this field, it can be noted that the polyhalide
metal complexes remain incomparably less explored. For the all-
polyhalide complexes, single examples are known for
polyiodides8-11 and polybromides.12-17 Coordination of mixed
In this work, we present
a new family of polymeric
polyiodo(bromo)antimonates (III) belonging to four different
structural types, exemplified by (Me4N)3{α-[Sb2Br9](I2)} (1), (4-
MePyH)3{β-[Sb2Br9](I2)} (2), and (BPE){[SbBr5](I2)} (3) (BPE =
N,N-bis-(Py)ethane cation), as well as their optical features
(photoconductivity) and theoretical insights into the nature and
energy of I···Br contacts.
[a]
Dr. S.A. Adonin, Ms. L.I. Udalova, Dr. P.A. Abramov, Ms. I.V.
Yushina, Dr. I.V. Korolkov, Dr. E.Yu. Semitut, Prof. Dr. M.N.
Sokolov, Prof. Dr. V.P. Fedin
Nikolaev Institute of Inorganic Chemistry SB RAS
630090 Lavrentieva St. 3, Novosibirsk, Russia.
E-mail: adonin@niic.nsc.ru
Dr. S.A. Adonin, Ms. L.I. Udalova, Dr. P.A. Abramov, Dr. I.V.
Korolkov, Prof. Dr. M.N. Sokolov, Prof. Dr. V.P. Fedin
Novosibirsk State University
630090 Pirogova St. 2, Novosibirsk, Russia
Dr. A.S. Novikov
[b]
[c]
Results and Discussion
Institute of Chemistry
Saint Petersburg State University
For preparation of 1-3, we have applied the approach developed
for synthesis of polybromometalates earlier:22 HBr solutions of
bromides of various cations were added to the HBr solutions
containing [SbBr6]3- and dissolved I2. Considering lesser
hydrolytic stability of [SbBr6]3- in comparison with [BiBr6]3-, higher
concentrations of HBr were used (see Experimental Section). In
some cases, formation of crystalline products succeeded only if
resulting mixtures were cooled (see below). In total, over 20
cations were tested; the list of experiments is given in SI. It can
be seen that in many cases there form crystalline solids of
quality insufficient for XRD. The dark color itself indicates the
199034 Universitetskaya Nab. 7-9, Saint Petersburg, Russia
Dr. T.A. Derzhavskaya, Prof. Dr. P.A. Troshin
Institute for Problems of Chemical Physics RAS
142432 Semenov ave. 1, Chernogolovka, Russia
Prof. Dr. K.J. Stevenson, Prof. Dr. P.A. Troshin
Skolkovo Institute of Science and Technology
121205 Nobelya St. 3, Moscow, Russia
[d]
[e]
Supporting information for this article is given via a link at the end of
the document.
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10.1002/chem.201802100
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presence of polyiodide, but not haloantimonate (in several
experiments, we isolated polyiodide or polyiodobromide salts of
corresponding organic cations).
2.855-2.948 and 2.913 Å, Br-I-I = 174.48-177.50 and 175.84° for
Cu33 and Pd,20 respectively). Each {BrI2} unit has longer contacts
with one of the Br ligands of another {SbBr4(BrI2)} moiety (I···Br
= 3.621(1) Å), forming a linear chain (Figure 2). The distances
between {I2} and Sb in neighboring chains exceed the sum of
van der Waals radii (4.04 vs 4.186(1)-4.235(1)Å).
Compounds 1 and 2 reveal the same composition of the anionic
part, as well as certain structural similarity. In both cases, the
main “building blocks” are binuclear {Sb2Br9} (two {SbBr6}
octahedra sharing one face) which were found in several
bromoantimonates (III) earlier;30-32 the average Sb-Brterm and Sb-
μ2-Br bonds are similar to those found in [Sb2Br9]3- salts
(2.633(1), 3.041(1) and 2.666(1), 3.060(1) Å in 1 and 2,
respectively). The structural feature of both 1 and 2 is the
presence of “trapped” {I2} which participate in specific
interactions with the terminal bromide ligands of {Sb2Br9}, thus
forming one-dimensional chains. The Brterm-I distances are
3.145(1) in 1 and 3.461(1) Å in 2, being clearly less than the
sum of Bondi’s (the shortest) van der Waals radii for Br and I
(3.81 Å). As in the case of the Bi(III) polybromides,22 this justifies
proposing the existence of specific supramolecular contacts
between these units. The difference between the {[Sb2Br9](I2)}
substructures in 1 and 2 is the mutual orientation of {I2} and
{Sb2Br9}, resulting in two various types of the chain structure,
which might be described as transoid (1) and cisoid (2) isomers
of the polymeric chain (Figure 1). The cisoid binding mode was
found earlier in polybromide complexes of Bi(III)22, and in the
single known example of polybromoantimonate (III), while the
transoid mode has not been reported before.
Figure 2. One-dimensional chains in 3. Sb blue, Br olive-green, I purple, I···Br
contacts dashed
Topological analysis of the electron density distribution within
the formalism of Bader's theory (QTAIM method)34 is an efficient
tool for the studies of various non-covalent interactions in
different complexes.35-38 Details of calculations for 1-3 are
summarized in Table 4S (SI). To visualize the non-covalent
interactions, reduced density gradient (RDG) analysis was
carried out;39 RDG isosurfaces were plotted (Figures 4 and 5). In
all cases, QTAIM analysis demonstrates the presence of
appropriate bond critical points (BCPs) (3, –1) for different non-
covalent interactions (Table 4S).
Figure 1. Interactions between {Sb2Br9} and I2 units in 1 (top) and 2 (bottom).
Sb blue, Br olive-green, I purple, Br···I contacts dashed
Another structural type of polyiodo(bromoantimonate) was found
in 3, possessing a number of interesting features. First, the
coordination number of Sb(III) is lower: each Sb is surrounded
by five bromide ligands, forming a severely distorted tetragonal
pyramid. All the Sb-Br distances are non-equal: the unusually
short one (2.5347(6) Å) corresponds to the Br ligand located
trans to the lone pair. Three Sb-Br bonds fit within the usual
range (2.6375(5)-2.8334(5) Å). The most remote Br ligand (Sb-
Br = 2.9784(5) Å) is connected with {I2} unit. The I···Br distance
is 2.9534(5) Å (Br-I-I = 174.6°), and this observation allows us
postulating the presence of rare BrI2- ligand. According to the
CSD data, in both known cases where coordination of {BrI2} was
observed, the geometry of this fragment was comparable (Br-I =
Figure 4. Contour line diagrams of the Laplacian distribution 2(r), bond
paths and selected zero-flux surfaces (left) and RDG isosurfaces (right)
referring to different non-covalent interactions in 1 (I···Br – top) and 3
(bifurcated I···Sb···I – bottom). Bond critical points (3, –1) blue, nuclear critical
points (3, –3) pale brown, ring critical points (3, +1) orange. Length units – Å,
RDG isosurface values are given in Hartree.
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units.46 In order to reveal the potential of the designed
compounds as electronic materials, their thin films are
incorporated in the lateral two-electrode device geometry (Figure
6a) and probed for existence of any semiconductor behavior and
photoconductivity effects. It should be emphasized that growing
thin films was a very challenging task considering the fact that 1-
3 can hardly be solubilized in organic or inorganic solvents
without complete degradation. Nevertheless, we found that
solution of Me4NBr, SbBr3 and I2 (I2 should be taken in 3-4 fold
excess compared to the stoichiometric amount) in anhydrous
CH2Cl2 is rather stable and can be drop-casted to produce thin
crystalline film of 1. Interestingly, spin-coating did not work
resulting in the formation of iodine-free complex antimony
bromides.
Figure 5. Contour line diagram of the Laplacian distribution 2(r), bond paths
and selected zero-flux surfaces (left) and RDG isosurface (right) referring to
I···Br non-covalent interactions in 2. Bond critical points (3, –1) blue, nuclear
critical points (3, –3) pale brown. Length units – Å, RDG isosurface values are
given in Hartree.
Two types of short halogen–halogen contacts are usually
discussed in the literature (see figure in SI).40,41 Type I is
believed to depend on the effects of crystal packing, while type II
is due to a classic halogen bonding (XB) (a halogen atom with a
90° angle provides its lone pair for interaction and the other one
provides its σ-hole). The non-covalent interactions I···Br in 1, 2,
and 3 can be attributed as type I contacts.
Figure 6b shows the current-voltage characteristics of the lateral
two-electrode device with the active film of 1 measured in the
dark and under illumination with the violet light (405 nm, ~70
mW/cm2, diode laser). One can clearly see that the current
increases by almost two orders of magnitude under illumination
(see also log plot in SI), thus manifesting relatively strong
The low magnitude of the electron density (0.004–0.033 Hartree),
positive values of the Laplacian (0.014–0.061 Hartree), and
close-to-zero energy density (–0.003–0.001 Hartree) in these
BCPs are typical for non-covalent interactions. We extracted the
energies of these contacts according to the previously proposed
procedures,42,43 and can state that strength of these non-
covalent interactions varies from 0.6 to 6.9 kcal/mol. The
balance between the Lagrangian kinetic energy G(r) and
potential energy density V(r) at the BCPs (3, –1) reveals the
nature of these interactions: if the ratio –G(r)/V(r) > 1 is satisfied,
then the interaction is purely non-covalent, if the –G(r)/V(r) < 1,
there is some covalent component.44 Based on this criterion we
state that many contacts listed in Table 4S allow some covalent
contribution. The nature of different non-covalent interactions in
1-3 was also analyzed based on the Wiberg bond indices
computed by using the natural bond orbital (NBO) partitioning
scheme.45 The values of the Wiberg bond indices for purely non-
covalent contacts I··Br in 2; I···Br and Sb···I in 3 are relatively
small (0.02–0.03), which also confirms the electrostatic nature of
these weak interactions, whereas for other contacts with some
covalent contributions (see Table 4S) the values of the Wiberg
bond indices are noticeable (0.11–0.22).
photoconductivity effect. This behavior suggests that
1
represents a promising semiconductor material for multiplication-
type photodetectors and, probably, also for “perovskite-inspired”
solar cells using complex metal halides as active layer materials.
Further research in that direction as well as exploration of
characteristics of 2 and 3 is currently in progress.
a
Au
Au
Polyiodo(bromoantimonate) 1
Substrate
8,0x10-9
b
dark
under illumination
4,0x10-9
0,0
-4,0x10-9
-8,0x10-9
-100
-50
0
50
100
According to the PXRD data (see SI), 1 and 3 can be isolated in
pure form (for 2, formation of unidentified by-products persists),
making detailed investigation of bulk samples possible.
Preliminary estimation of the optical band gaps for 1 and 3
resulted in values below 1.5 eV (see SI), making them promising
candidates for photovoltaic applications. An additional argument
in favor of their feasible practical use is their decent thermal
stability, which was studied by TGA (see SI): decomposition
related to the loss of diiodine starts at 100-150°C. Additionally,
we have recorded Raman spectra (see SI); in all cases, those
are consistent with symmetries of corresponding polyhalide
Voltage, V
Figure 6. Schematic layout of the lateral two-electrode device with compound
1 used as semiconductor (a). Current-voltage characteristics of the device
measured in dark and under violet light illumination (405 nm, 70 mW/cm2)
given in linear scale (b).
Conclusions
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operated with Advantest 6240A source-measurement unit. All devices
degraded completely under storage inside the glove box overnight, which
was accompanied by the color change of the active films from dark-red to
light-yellow suggesting decomposition of the polyiodide-bromoantimonate
with the formation of conventional Sb(III) halides. Devices also showed
noticeable degradation after each successive measurement suggesting
that the active material is sensitive to light and/or electric field.
Several points can be highlighted in conclusion. First, the simple
combination “dihalogen + hydrohalic acid” by itself represents a
potent virtual dynamic library which is applicable in inorganic
synthesis, resulting in cation-driven formation of numerous
polyhalides of different dimensionality. Considering the main
advantage of this system – simplicity of preparation, especially
in comparison with ionic liquids which are currently widely used
for the preparation of polyhalides – it certainly deserves to be
exploited further. Second, unlike bismuth, Sb adopts variable
coordination environment, adjusting to the crystal packing. This
feature appears to be due to the more pronounced activity of the
lone pair at Sb(III); although there are examples of square
pyramidal Sb compounds47,48 and such behaviour was reported
for haloantimonates (III), it is not very common.49 Also, this
feature was not yet observed in corresponding polybromides of
Sb(V) reported by us recently.50 Finally, increased dimensionality
of the designed complexes is manifested in their semiconductor
properties (similar observations were made for Pb(II)51 and
Bi(III)52 polyiodide hybrids) and strong photoconductivity effects,
featuring multiple potential applications in electronics and
photovoltaics.
Details of X-ray Diffractometry and computational details are given in
SI.
Acknowledgements
This work has been supported within the Skoltech-MIT Next
Generation Program. ASN also thanks Russian Foundation for
Basic Research (16-33-60063 – theoretical studies). SAA thanks
the President Grant Council for a personal research fellowship.
NIIC part of team thanks Federal Agency for Scientific
Organizations for support as well.
Keywords: polyhalide • halometalate • antimony •
photoconductivity • DFT calculations
Experimental Section
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General remarks. All experiments were carries out in air. BPE and 4-
EtBPE dibromides were obtained by reactions of pyridine or 4-
ethylpyridine with 1,2-dibromoethane (CH3CN, stirring, 12 h); purity was
confirmed by 1H NMR and element analysis.
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Preparation of 1-3. For 1, 50 mg (0.17 mmol) of Sb2O3 were dissolved
in 7 ml of concentrated HBr. Then, 44 mg of I2 were added; solution was
stirred for 1 h resulting in complete dissolution of I2. Then, solution of
Me4NBr (44 mg, 1.1x excess) in 2 ml of HBr was added and the mixture
was kept at 6°C for 12 h, resulting in formation of dark crystalline
precipitate. For 2–3, procedure was similar, using 4-MePy (28 mcl) in 2
ml HBr (2) or 88 mg of I2 (11 ml HBr) and BPEBr2 (118 mg in 4 ml) (3). In
all cases, yield was 81-85% (for 2 – estimated). Data of element analysis
are given in SI.
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Fabrication of the lateral two-electrode device with compound 1.
Glass slides (15x15 mm) were cleaned first in the base piranha solution
(25% aqueous NH3 + 30% H2O2, 4:1), then washed with deionized water,
dried with a stream of nitrogen and further treated with oxygen plasma for
7 min. Gold electrodes (200 nm) were deposited by thermal evaporation
in high vacuum (10-6 mbar) through the shadow mask defining the
device configuration: channel length of 80 µm and width of 2 mm. Each
glass slide had 4 pairs of electrodes. A solution of Me4NBr (63.9 mg),
SbBr3 (100 mg) and I2 (125 mg) in 1.0 mL of anhydrous CH2Cl2 was
prepared by stirring all components together at room temperature inside
MBraun glove box. The obtained solution was filtered through 0.45 µm
PTFE syringe filter (no visible precipitate detected in the filter) and drop-
casted above the channels between the gold electrodes. The solvent and
excess of I2 were evaporated at room temperature inside the glove box
leaving dark-red crystalline films of 1 (confirmed by EDX). The yield of
the working devices was ca. 25% as revealed by current-voltage
measurements in dark using Keithley 2612A instrument. Some devices
were showing zero currents (missing contact between the material and
the electrodes), while others were shorted probably due to partial
dissolution of gold in the drop-casted solution. The illumination for the
measurements was provided by violet diode laser (405 nm, ~70 mW/cm2)
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10.1002/chem.201802100
Chemistry - A European Journal
FULL PAPER
FULL PAPER
Photoconductive metal-polyhalide
hybrids: In presence of different
cations, reactions of [SbBr6]3- and I2
result in a family of polyiodide-
bromoantimonate networks.
Coordination number of Sb, as well
as geometry of assembling {BrxIy}n-
polyhalide units, varies, resulting in
unprecedented structural types.
Some of the compounds showed
strong photoconductivity in thin films,
suggesting multiple feasible
Dr. Sergey A. Adonin,* Ms. Liubov I.
Udalova, Dr, Pavel A. Abramov, Dr.
Alexander S. Novikov, Dr.Denis G.
Samsonenko, Ms. Irina V. Yushina, Dr.
Ilya V. Korolkov, Dr. Evgeniy Yu.
Semitut, Dr. Tatiyana A. Derzhavskaya,
Prof. Dr. Keith J. Stevenson, Prof. Dr.
Pavel A. Troshin, Prof. Dr. Maxim N.
Sokolov and Prof. Dr. Vladimir P. Fedin
Page No. – Page No.
A novel family of polyiodo-
bromoantimonate(III) complexes:
cation-driven self-assembly of
photoconductive metal-polyhalide
frameworks
applications in optoelectronics and
solar energy conversion.
This article is protected by copyright. All rights reserved.