Role of I2 Molecules and Weak Interactions in Supramolecular

Mar 20, 2018 - Department of Materials Sciences, Lomonosov Moscow State University, .... (17−20) More complex 1D structures were also described, for...
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Role of I2 Molecules and Weak Interactions in Supramolecular Assembling of Pseudo-Three-Dimensional Hybrid Bismuth Polyiodides: Synthesis, Structure, and Optical Properties of Phenylenediammonium Polyiodobismuthate(III) Tatiana A Shestimerova, Nikita A Golubev, Natallia A Yelavik, Mikhail A Bykov, Anastasia V Grigorieva, Zheng Wei, Evgeny V. Dikarev, and Andrei V. Shevelkov Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00179 • Publication Date (Web): 20 Mar 2018 Downloaded from http://pubs.acs.org on March 20, 2018

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Crystal Growth & Design

Role of I2 Molecules and Weak Interactions in Supramolecular Assembling of Pseudo-Three-Dimensional Hybrid Bismuth Polyiodides: Synthesis, Structure, and Optical Properties of Phenylenediammonium Polyiodobismuthate(III) Tatiana A. Shestimerova,† Nikita A. Golubev, † Natallia A. Yelavik, †,‡ Mikhail A. Bykov, † Anastasia V. Grigorieva,# Zheng Wei,§ Evgeny V. Dikarev, §,* and Andrei V. Shevelkov†,* †

Department of Chemistry, Lomonosov Moscow State University, Moscow, 119991, Russia

#

Department of Materials Sciences, Lomonosov Moscow State University, Moscow, 119991, Russia

§

Department of Chemistry, University at Albany, Albany, NY 12222, USA

KEYWORDS iodometallates; bismuth; polyiodide; crystal structure; intermolecular interactions; supramolecular architecture; optical properties ABSTRACT: Phenylenediammonium polyiodobismuthate(III), [PDA(BiI4)2·I2] (PDA = phenylenediammonium, [NH3C6H4NH3]2+), represents a new hybrid halometallate synthesized in a form of black well-shaped crystals by a facile reaction in aqueous solution of HI containing dissolved I2. It crystallizes in triclinic space group P-1 with the unit cell parameters a = 7.761(1), b = 9.259(1), c = 9.689(1) Å, α = 95.68(3), β = 103.19(3), γ = 93.56(3)o, and Z = 1. Its crystal structure comprises three levels of organization discriminated by a type of chemical bonding. The first level is provided by covalently bonded [BiI6] octahedra linked into [BiI4]∞– one-dimensional anionic chains; the second level features secondary bonds between the chains and I2 bridging molecules; whereas the third level is specified by the weak hydrogen N–H···I bonds involving diammonium cation and I···I intermolecular interactions that additionally link anionic chains. Altogether, these three interaction types ensure the formation of a complex pseudo-three-dimensional crystal structure. According to optical absorption study, [PDA(BiI4)2·I2] is a semiconductor with the band gap of 1.45 eV.

Introduction The discovery of photovoltaic efficiency in methylammonium lead iodide1 boosted the research into synthesis and optical properties of various inorganic and hybrid haloplumbates2-4. Although some representatives of this family combine high photovoltaic efficiency of 22% with the ease of fabrication from solutions of common solvents, the presence of toxic lead raises concerns regarding widespread applications of these materials as light-harvesters and have already led to identification and evaluation of lead-free perovskite-like materials5-7. No surprising, a search for nontoxic, soluble halide semiconductors for replacement of lead-based compounds has been initiated with scrutinizing complex tin halides8-10. The latter complexes demonstrated the efficiency approaching 10%, but very low stability caused by easy oxidation of SnII in air or its disproportionation upon moderate heating in inert atmosphere. Another promising direction of search for prospective light-

harvesting halide semiconductors is represented by bismuth compounds. Bismuth is known to form iodides and iodocomplexes of two types. In the low oxidation states (between 0 and +2), bismuth yields cluster iodides of different structural organization, which contain the Bi–Bi bonds11-13. In the oxidation state of +3 bismuth forms a number of complex iodides, all of which are based on [BiI6] octahedra as building units14-16. The most common feature of the crystal structures of iodobismuthates is the presence of isolated anions [BiI6]3–, [Bi2I10]4–, or [Bi2I9]3–, whose negative charge is compensated by various inorganic and organic cations. High-nuclearity Bi/I anions that involve 3 to 10 [BiI6] edge/face-sharing octahedra are also known, but those are rare14,16. Also reported are 1D or 2D arrangements of [BiI6] octahedra. The chains formed by sharing edges or vertices are quite common in the crystal chemistry of iodomismuthates; they all show a certain degree of [BiI6] disorder caused by longer

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Bi–I bonds to bridging iodine atoms compared to terminal ones17-20. More complex 1D structures were also described, for example, a peculiar strand-like anion [Bi6I20]2– showing the lowest I/Bi ratio of 3⅓ of all chain-like anions21. At the same time, only a single type of a 2D anionic substructure was found for iodobismuthates. It is exemplified by the Rb3Bi2I9 structure type that comprises only four compounds, in which [BiI6] octahedra share four vertices to form layers that can be viewed as a perovskite-type layer with ⅓ of metal positions remaining vacant15, 22. Obviously, [BiI6] octahedra alone cannot be arranged into a 3D array, since BiI3 itself is a neutral compound formed by the edge-shared [BiI6] units23. However, in numerous iodobismuthates, intermolecular bonding between Bi–I moieties is provided through I···I contacts from neighboring anions as well as by hydrogen bonds of the O–H···I and N–H···I types that are capable to link the anions into 3D supramolecular structures19. Another possible tool for linking of [BiI6] octahedra is represented by interstitial I2 molecules acting as bridges24. In this case, I2 moieties combine [BiI6] octahedra into extended architectures by alternating shorter covalent and longer secondary bonds, similar to those structural patterns in various other polyiodides25. The arrangement of [BiI6] octahedra into an extended structure is a prerequisite for constructing light-harvesting materials of all-solid solar cells; therefore, the design and synthesis of bismuth poyiodides with extended structures are of great importance26. Herein we report on the synthesis, crystal structure, and properties of a new compound [PDA(BiI4)2·I2] (PDA = phenylenediammonium, [NH3C6H4NH3]2+) that features 1D iodobismuthate anions linked into a 2D structure by interstitial I2 molecules through polyiodide bonding and ultimately assembled into a 3D motive via intermolecular interactions. Experimental Section Synthesis. Used as starting materials were Bi (granules, 99.99%), I2 (analytical grade), phenylenediamine (analytical grade), and HI 57% water solution (pure). BiI3 was synthesized from the elements as described elsewhere17. For the preparation of title compound [PDA(BiI4)2·I2], 4 ml of aqueous solution containing 57 wt.% of a mixture of HI and I2 in a molar ratio of 1:1 was added to the starting reagents taken in a molar ratio of BiI3:PDA = 2:1 with a total weight of 0.1 g. The flask with the resulting solution was kept in a bain-marie at the temperature of 45 °C for 30 min, and then it was left for evaporation in

open air for two months to yield black well-shaped crystals. Thermal analysis. Thermogravimetric analysis was performed using a NETZSCH 209 F1 Libra thermobalance. Calibration performed with CaC2O4·2H2O showed that the accuracy of mass detection was better than 0.1%. Heating of the samples was done in alumina crucibles under dry nitrogen flow up to 450 oC with the ramp rate ranging from 5 to 10 K·min–1. The NETZSCH Proteus Thermal Analysis program was used for the data processing. Powder X-ray diffraction analysis (PXRD) was performed on a Imaging Plate Guinier Camera (Huber G670, Cu-Kα1 radiation, λ = 1.540598 Å) with the 2θ ranging from 3 to 100° at a 0.005° increment. The data were collected by scanning the image plate 4 times after an exposure time of 1200 s at room temperature. For the analysis, crystals of [PDA(BiI4)2·I2] were finely crushed in an agate mortar, and the resulting powder was fixed on a holder using a scotch tape. Crystal structure determination. Single crystals of [PDA(BiI4)2·I2] were selected directly from reaction products. The single crystal diffraction data were measured at 100 K on a Bruker D8 VENTURE with PHOTON 100 CMOS detector system and graphite monochromator equipped with a Mo-target X-ray tube. A frame width of 0.50o and an exposure time of 15 s/frame were employed for data collection. Data reduction and integration were performed with the Bruker software package SAINT (Version 8.38A)27. Data were corrected for absorption effects using the semi-empirical methods (multi-scan) as implemented in SADABS (Version 2014/5)28. The crystal structure was solved by the direct methods using the SHELXTL (Version 2017/1) program package29, which gave positions of bismuth and iodine atoms. Positions of nitrogen and carbon atoms as well as of hydrogen atoms of the aromatic ring were found from successive difference Fourier syntheses, whereas those of hydrogen atoms of the NH3 groups were calculated and further refined using riding models. In the final step, the crystal structure was refined with anisotropic approximations of atomic displacement parameters for all non-hydrogen atoms. The crystal data are given in Table 1, and important interatomic distances in Table 2. Structure refinement parameters and atomic parameters are given in Tables S1 and S2 of Supporting Information. Further details on the crystal structure investigation may be obtained from the Cambridge Crystallographic Data Centre by quoting the CCDC number 1588608.

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Crystal Growth & Design Table 1. Crystal Data of [PDA(BiI4)2·I2]. Crystal system

Triclinic

Space Group

P-1

a, Ǻ

7.761(1)

b, Ǻ

9.259(1)

c, Ǻ

9.689(1)

α,°

95.68(3)

β,°

103.19(3) 93.56(3)

γ,° V, Ǻ

3

672.1(2)

Z

1

dcalc

4.440

R/Rw

0.0191/0.0343

(I> 4σ(I))

Table 2. Important Bonding Distances in the Crystal Structure of [PDA(BiI4)2·I2]. Atoms

Distance, Å

Atoms

Distance, Å

N1–H1A

0.91

–H1B

0.91

3.163(1)

–H1C

0.91

3.1988(7)

–C2

1.473(4)

Bi1– bridging iodine –I2 –I3

3.031(1) 3.3363(9)

terminal iodine –I4

2.9642(7)

–I5

2.8915(8)

I–I molecular I6–I6

2.7286(9)

intermolecular I2···I6

N1–H1A···I4

2.746(1)

–H1C···I4

2.8012(9)

C4–H2

0.89(4)

–C2

1.390(4)

–C3

1.383(5)

C2–C3 3.532(1)

interchain

–C4 C3–H3

I2···I4

3.837(1)

I5···I5

3.862(1)

2.736(1)

–H1B···I5

1.390(4) 1.392(4) 0.94(4)

Raman spectroscopy. Raman spectra of [PDA(BiI4)2·I2] were recorded on a Renishaw In Via spectrometer with laser wavelength of λ = 632.8 nm (Ar, 20 mW) with capacity varied via ND (neutral density) filters in an interval of 0.00005–100%. Sample investigation was performed in the back scattering geometry using a confocal microscope Leica DMLM (100´ lens) at room temperature in air. Focus distance was 250 mm, and the size of laser beam was 20 µm. The CCD-camera (1024×368 pixels) was used as a detector. The scale calibration was done using

monocrystalline silica (521.5 cm–1) as a standard sample. WiRE 3.4 software was used for data processing. Optical Spectroscopy. Optical diffuse reflectance spectra were recorded using a UV-vis spectrometer Perkin-Elmer Lambda 950 with an attached diffuse reflectance accessory. Measurements were performed at 298 K in the spectral range of 250–1200 nm, with the scanning rate of 2 nm/s using finely ground polycrystalline samples. The data were processed using the Kubelka-Munk theory approximation and linearized in the [(k/s)·hυ]1/2 – (hυ) coordinates with hν along the x axis and [(k/s)·hν]1/2 along the y axis, where k is the absorption coefficient, s is the scattering coefficient, and h is the Planck constant30. The k/s relation known as a remission function was calculated using the refraction data according to the literature as k/s = (1–R)2/2R, where R is the absolute diffuse reflectance31. Extrapolation to k = 0 gives an approximate value of optical Eg of the material. Results and Discussion A reaction of bismuth(III) iodide with an aqueous solution of HI containing dissolved I2 taken in an equimolar ratio afforded a new compound [PDA(BiI4)2·I2] (PDA = phenylenediammonium, [NH3C6H4NH3]2+) in a form of well-shaped black crystals. The compound is stable in moist air within weeks of storage. Purity of the product was confirmed by X-ray powder diffraction analysis by comparison of experimental powder pattern with the one calculated from the single crystal data (see Supporting Information, Figure S1). The compound remains intact at the temperatures up to 100 oC. Heating [PDA(BiI4)·I2] under dry argon flow above this temperature leads to its decomposition which proceeds via liberation of I2 and organic residues, until pure BiI3 remains as a solid residue at about 350 oC (see Supporting Information, Figure S2). However, at such temperatures bismuth triiodide is volatile and is slowly carried away to the gas phase by flowing argon. The [PDA(BiI4)2·I2] crystallizes in the triclinic space group P–1 with one formula per unit cell (Table 1) and consists of three principal structural moieties (Table 2): a PDA cation, an infinite [BiI4]∞– anionic chain, and an I2 molecule present in a 1:2:1 ratio (Figure 1). The [BiI4]∞– chains run along the a direction of the unit cell. They are composed of [BiI6] octahedra that share their edges in such a fashion that two cisiodine atoms in each unit remain terminal (Figure S3). The octahedra are distorted in accord with a different character of iodine atoms. The Bi–I distances to terminal iodine atoms are predictably shorter (2.89–2.96 Å) than those to bridging ones (3.03–3.34

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Å). In addition, the I–Bi–I bond angles slightly deviate from 90 and 180 degrees, which is typical for various iodobismuthates containing [BiI4]∞– chain anions17-20.

F igure 1. A view of the crystal structure of [PDA(BiI4)2·I2] along the c axis. [BiI6] octahedra, magenta; diiodine, cyan; nitrogen, blue; carbon, light gray; hydrogen atoms are omitted for clarity. The PDA cations and I2 molecules alternate along the a axis forming a supramolecular arrangement running parallel to the [BiI4]∞– chains (Figure 1). The cation is planar with C–C and N–C distances of 1.38– 1.39 and 1.47 Å, respectively, typical of aromatic amines. The I–I distance within the I2 molecule is 2.73 Å, being only 0.01 Å longer than that in the molecular iodine at a temperature of 110 K32, which is only 10 K higher than what used in this work for the structural investigation. The I2 molecules are not aligned parallel to the aromatic rings of PDA cations. Apparently, this misalignment arises from intermolecular contacts between I2 and iodine atoms of the [BiI6] octahedra forming [BiI4]∞– anionic chains, whereas interaction of diiodine with the π-system of the aromatic ring is negligible, if present at all. The intermolecular I2···I([BiI6]) separation is 3.53 Å, and the I···I–I angle is 170 degrees. Another important intermolecular bonding is observed between the PDA cations and [BiI4]∞–chains through N–H···I contacts that range from 2.75 to 2.82 Å. Finally, there are I···I interactions of 3.84 and 3.86 Å between parallel anionic chains. The intermolecular I2···I([BiI6]) interactions of 3.53 Å are comparable to the shortest intermolecular interaction within the layers of solid diiodine, 3.50 Å32.

According to Svensson and Kloo25, such interatomic contact should be regarded as a secondary bond that is significantly stronger than the van-der-Waals interaction at a distance of 3.9 Å or longer. It should be noted that rather distant interatomic contacts in solid iodine, from 3.50 Å (intralayer) to 4.27 Å (interlayer), divert properties of molecular diiodine such that violet molecular gaseous I2 turns into a gray solid with a metallic luster and electrical conductivity typical of semiconductors. The latter is accompanied by a noticeable shift of a Raman frequency from 214 cm– 1 in gaseous molecular iodine to 180 cm–1 in the solid state33,34. Raman spectrum of the [PDA(BiI4)2·I2] (Figure 2) exhibits two peaks at 128 and 141 cm–1 that can be assigned to the Bi–I bridging and terminal bonds, respectively, analogous to a number of other iodobismuthates that show Raman shifts between 125 and 145 cm–1 17, 35. The peak at 180 cm–1 is assigned to I–I stretching, showing up at the same energy as in the solid diiodine, which is not surprising given that the I–I covalent and I···I secondary bond distances are almost the same in two compounds. According to the literature36, the I–I stretching in polyiodides shows up in a wide range of wavenumbers, from 110 to 190 cm–1, largely depending on the degree of the involvement of I2 molecules in bonding with other iodine atoms and anions. For instance, the I–I interaction in diiodine with the bond length of 2.76 Å was observed at 158 cm–1 in Cs2[PdI4]I2, where I2 molecules are involved in the coordination environment of Pd37. Lower Raman shifts observed at 106, 93, and 74 cm–1 (Figure 2) can be assigned to the I···I intermolecular interactions as well as to bending modes, although an unambiguous assignment of each particular frequency seems hardly possible.

Figure 2. Raman spectrum of [PDA(BiI4)2·I2]. See text for the detailed assignment of stretching frequencies.

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Crystal Growth & Design

Figure 3. Assembling of the I2 molecules and [BiI4]∞– chains into a layers through I(2)···I(6) interactions (dashed lines) in the crystal structure of [PDA(BiI4)2·I2]. A projection onto bc plane (top) and a view of one layer (bottom). Only bismuth (red) and iodine (light blue) atoms are shown for the sake of clarity. The N–H···I hydrogen bonds of 2.75–2.82 Å are visibly shorter than those typically observed in various iodobismuthates, ranging from 2.87 to 3.41 Å14,19, whereas the I···I interchain contacts of 3.84-3.86 Å are only slightly shorter that the expected van-derWaals contacts of 3.9 Å. 25 The literature analysis shows19, 38–40 that the I···I intermolecular interactions vary from 3.70 to more than 4 Å in hybrid iodobismuthates. Other intermolecular contacts include C–H···I (3.29–3.83 Å), N–H···I (3.39–3.84 Å), and C···I (3.74 Å). However, those are quite distant and surpass the respective sums of the van-der-Waals radii. The overall structural organization based on covalent and supramolecular bonding deserves further discussion. The [BiI4]∞– chains build a 1D covalent substructure. Similar chains that run parallel to each other are frequently observed in io-

domismuthateswith a variety of organic and inorganic cations17–20,41,42. As a rule, in such structures, bismuth atoms are bonded only to iodine atoms, whereas the covalent interaction of bismuth with cations is a rare exception43, 44. The I2 molecules unite these chains into layers through the intermolecular bonding thus forming a 2D substructure shown in Figure 3. The literature provides examples of iodobismuthates mainly organized into polymer structures with the help of a number of hydrogen bonds linking a Bi/I substructure to various organic cations19. Scarce alternatives are presented by compounds incorporating the I2 moieties that “stitch” [BiI6] octahedra into polymeric structures by relatively strong I–I bonds with interatomic distances of as short as 3.35 Å24. In the crystal structure of PDA(BiI4)2·I2, the intermolecular I···I distance is significantly longer, 3.53 Å, resembling rare examples of bismuth polybromide complexes, in which the Br···Br interatomic distance is nearly 1 Å longer than the Br– Br covalent bond length45, 46. On the other hand, the I···I distance is noticeably shorter than the sum of van-der-Waals radii (3.9 Å). Therefore, the observed I···I2···I fragments with the interatomic distances of 3.53 Å (I···I) and 2.73 Å (I–I) can be viewed as a portion of the structure of metallic iodine where covalent and intralayer distances of 2.72 and 3.50 Å, respectively, are almost the same as in PDA(BiI4)2·I2. Bonding between the layers is provided through hydrogen bonds of the N–H···I type (2.72–2.85 Å). In addition, the I···I interchain interactions of 3.84 and 3.86 Å that are still shorted than the doubled vander-Waals radius of iodine should be taken into account. Together, these weak interactions provide further links between the layers, leading to the 3D structure presented in Figure 4. Therefore, the crystal structure of PDA(BiI4)2·I2 provides the first example of combining covalent Bi–I and secondary I···I bonding with hydrogen N–H···I and intermolecular I···I bonding for building up a 3D framework featuring both covalent and supramolecular bonds. We note that the description of the 3D structure assembling does not involve consideration about the strength of non-covalent bonds. In fact, the energy of secondary and intermolecular I···I may vary from 1-2 to 20-25 kJ mole–1 depending on the bond length, whereas the strength of the N–H···I hydrogen bond may reach 25 kJ mole–1. 47, 48 Optical absorption was measured using a polycrystalline powder sample. PDA(BiI4)2·I2 is black, which corresponds well to the band gap of 1.45 eV extracted from the Kubelka-Munk plot (Figure 5). According to

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our previous quantum-chemical calculations, charge transfer in bismuth iodides and polyiodides proceeds from 5p orbitals of iodine forming the top of the valence band to 6s orbitals of bismuth at the bottom of the conduction band17. In the case when I2 moieties are present, they contribute mainly to the top of valence band leading to lowering of the band gap and ensuring efficient absorption of light across the solar spectrum, which is a necessary condition for lightharvesting materials of all-solid perovskite solar cells.

Figure 4. Projection of the crystal structure of [PDA(BiI4)2·I2] onto bc plane. [BiI6] octahedra, magenta; diiodine, cyan; nitrogen, blue; carbon, light gray; hydrogen, dark gray. Intermolecular I···I and N–H···I interactions are shown as dashed lines.

[PDA(BiI4)2·I2] (PDA = phenylenediammonium, [NH3C6H4NH3]2+) is a new hybrid bismuth polyiodide. It has a complex crystal structure that features three different levels of structural organization with progressive lowering of the bond strengths. At the first level, [BiI6] octahedra condense into [BiI4]∞– anionic chains through strong Bi–I covalent bonds. The second level is provided by I2 molecules that bridge the chains through the secondary I···I bonds of 3.53 Å thus forming layers. At the third level, the layers are assembled into a three-dimensional architecture by N–H···I hydrogen bonds that involve PDA cations as well as the interchain I···I interactions that are slightly shorter than van-der-Waals separations between iodine atoms. The I2 molecules display the Raman frequency similar to that observed for solid diiodine reflecting the striking similarity of the respective I–I covalent and secondary I···I bond lengths between the title compound and solid I2. The title compound is black and shows an optical band gap of 1.45 eV with the low forbidden gap width resulting from the apparent involvement of orbitals of the bridging I2 molecules in the ligand-to-metal charge transfer across the band gap. Based on the crystal structure, relative stability, and optical properties, we speculate that the reported bismuth polyiodide may appear as promising light-harvester for all-solid solar cells and that supramolecular assembling through the combination of secondary and intermolecular bonds may emerge as a powerful tool for assembling three-dimensional structures based on Bi-I anions. ASSOCIATED CONTENT Supporting Information. Structure refinement details, table of atomic parameters, – XRD pattern, thermal analysis data, and a view of the [BiI4]∞ chains (PDF). This material is available free of charge via the Internet at http://pubs.acs.org. Accession Codes CCDC 1588608 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

AUTHOR INFORMATION Corresponding Authors

* Authors for correspondence: [email protected] (EVD) and [email protected] (AVS.) ORCID

Figure 5.Kubelka-Munk [PDA(BiI4)2·I2] Conclusions

plot

for

Andrei V. Shevelkov: 0000-0002-8316-3280 Evegeny V. Dikarev: 0000-0001-8979-7914 PresentAddresses

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Crystal Growth & Design ‡ Present address: Faculty of Technical Chemistry, Technical University of Vienna, Getreidemarkt 9, 1060 Wien, Austria Author Contributions

All authors have given approval to the final version of the manuscript. Funding Sources

The research of Moscow team has been supported by the Russian Ministry of Education and Science, contract No. RFMEFI61316X0053 (14.613.21.0053). The work of Albany team has been funded by the National Science Foundation, grant No. CHE-1152441.

Notes

The authors declare no competing financial interest

ABBREVIATIONS PDA, phenylenediammonium.

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Role of I2 Molecules and Weak Interactions in Supramolecular Assembling of Pseudo-ThreeDimensional Hybrid Bismuth Polyiodides: Synthesis, Structure, and Optical Properties of Phenylenediammonium Polyiodobismuthate(III) Tatiana A. Shestimerova, Nikita A. Golubev, Natallia A. Yelavik, Mikhail A. Bykov, Anastasia V. Grigorieva, Zheng Wei, Evgeny V. Dikarev, and Andrei V. Shevelkov

Phenylenediammonium polyiodobismuthate(III), [PDA(BiI4)2·I2], displays three levels of structural organization. At – the first level, covalent bonds link [BiI6] octahedra into [BiI4]∞ anionic chains. The second level is provided by I2 molecules that bridge the chains into layers through secondary bonds. Finally, intermolecular and hydrogen bonds ensure assembling of layers, leading to a 3D supramolecular structure.

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