Testing the tools for revealing and characterizing the iodine–iodine halogen bond in crystals

Барташевич, Е. В.; Yushina, I. D.; Kropotina, Kristina; Muhitdinova, Svetlana; Tsirelson, Vladimir G.

doi:10.1107/s2052520617002931

“…. I and other interactions in the studied crystals from the calculated electron density and electrostatic potential point of view as this approach has already been proven to be demonstrative [59,60]. Figure 4 illustrates the examples of S .…”

Section: Noncovalent Bonds Formed By Triiodide Anions: Electron Densimentioning

confidence: 82%

“…The examples of the main considered S…I interactions in the studied crystals are presented in Figure 3 and Figure 4. Let us consider the S…I and other interactions in the studied crystals from the calculated electron density and electrostatic potential point of view as this approach has already been proven to be demonstrative [59,60]. Figure 4 illustrates the examples of S…I chalcogen bonds in the considered crystals as well as the verification of non-covalent bonding type based on the electronic criteria.…”

Section: Noncovalent Bonds Formed By Triiodide Anions: Electron Densimentioning

confidence: 99%

Noncovalent Bonds, Spectral and Thermal Properties of Substituted Thiazolo[2,3-b][1,3]thiazinium Triiodides

Yushina

¹

,

Тарасова

²

,

Kim

³

et al. 2019

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The interrelation between noncovalent bonds and physicochemical properties is in the spotlight due to the practical aspects in the field of crystalline material design. Such study requires a number of similar substances in order to reveal the effect of structural features on observed properties. For this reason, we analyzed a series of three substituted thiazolo[2,3-b][1,3]thiazinium triiodides synthesized by an iodocyclization reaction. They have been characterized with the use of X-ray diffraction, Raman spectroscopy, and thermal analysis. Various types of noncovalent interactions have been considered, and an S…I chalcogen bond type has been confirmed using the electronic criterion based on the calculated electron density and electrostatic potential. The involvement of triiodide anions in the I…I halogen and S…I chalcogen bonding is reflected in the Raman spectroscopic properties of the I–I bonds: identical bond lengths demonstrate different wave numbers of symmetric triiodide vibration and different values of electron density at bond critical points. Chalcogen and halogen bonds formed by the terminal iodine atom of triiodide anion and numerous cation…cation pairwise interactions can serve as one of the reasons for increased thermal stability and retention of iodine in the melt under heating.

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“…[1] Their structural diversity,which is due to the bonding flexibility of iodine,r emains the subject of continuous interest. [8] Furthermore,t he energy den- Their building blocks consist of I 3 À as adonor and I 2 as an acceptor forming ac harge transfer (CT) complex.…”

mentioning

confidence: 99%

Pressure‐Induced Polymerization and Electrical Conductivity of a Polyiodide

Poręba

¹

,

Ernst

²

,

Zimmer³

et al. 2019

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We report the high-pressure structural characterization of an organic polyiodide salt in which ap rogressive addition of iodine to triiodide groups occurs.C ompression leads to the initial formation of discrete heptaiodide units, followed by polymerization to a3Danionic network. Although the structural changes appear to be continuous,t he insulating salt becomes as emiconducting polymer above1 0GPa.T he features of the pre-reactive state and the polymerized state are revealed by analysis of the computed electron and energy densities.T he unusually high electrical conductivity can be explained with the formation of new bonds.Polyiodides (PIs) in crystal form were discovered about 200 years ago. [1] Their structural diversity,which is due to the bonding flexibility of iodine,r emains the subject of continuous interest. [2][3][4] Nowadays,v arious PIs are known, ranging from I 3 À to I 29 3À ,with the general formula I nÀ 2 m+n and n up to 4. Their building blocks consist of I 3 À as adonor and I 2 as an acceptor forming ac harge transfer (CT) complex. CT complexes can interact further to form extended structures with various topologies,u pt oc ubic networks.A st he aggregation of iodine units is somewhat unpredictable,t he design of PIs is not easy.Moreover,the classification of higher units is,thus far,pragmatically based on the distance between iodine atoms,but universal criteria are still lacking.Different theoretical approaches to study bonds in PIs exist, for example,calculations of the potential energy surface and bond order, [5] energy decomposition analysis (EDA), [6] analysis of the electron density and its Laplacian at bond critical points (BCP), [7] theelectron localization function, and the one-electron potential. [8] Furthermore,t he energy den-

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“…Different theoretical approaches to study bonds in PIs exist, for example, calculations of the potential energy surface and bond order, energy decomposition analysis (EDA), analysis of the electron density and its Laplacian at bond critical points (BCP), the electron localization function, and the one‐electron potential . Furthermore, the energy densities at BCPs and the interacting quantum atom (IQA) method were used to analyze halogen bonds …”

Section: Figurementioning

confidence: 99%

Pressure‐Induced Polymerization and Electrical Conductivity of a Polyiodide

Poręba

¹

,

Ernst

²

,

Zimmer

³

et al. 2019

View full text Add to dashboard Cite

We report the high-pressure structural characterization of an organic polyiodide salt in which ap rogressive addition of iodine to triiodide groups occurs.C ompression leads to the initial formation of discrete heptaiodide units, followed by polymerization to a3Danionic network. Although the structural changes appear to be continuous,t he insulating salt becomes as emiconducting polymer above1 0GPa.T he features of the pre-reactive state and the polymerized state are revealed by analysis of the computed electron and energy densities.T he unusually high electrical conductivity can be explained with the formation of new bonds.Polyiodides (PIs) in crystal form were discovered about 200 years ago. [1] Their structural diversity,which is due to the bonding flexibility of iodine,r emains the subject of continuous interest. [2][3][4] Nowadays,v arious PIs are known, ranging from I 3 À to I 29 3À ,with the general formula I nÀ 2 m+n and n up to 4. Their building blocks consist of I 3 À as adonor and I 2 as an acceptor forming ac harge transfer (CT) complex. CT complexes can interact further to form extended structures with various topologies,u pt oc ubic networks.A st he aggregation of iodine units is somewhat unpredictable,t he design of PIs is not easy.Moreover,the classification of higher units is,thus far,pragmatically based on the distance between iodine atoms,but universal criteria are still lacking.Different theoretical approaches to study bonds in PIs exist, for example,calculations of the potential energy surface and bond order, [5] energy decomposition analysis (EDA), [6] analysis of the electron density and its Laplacian at bond critical points (BCP), [7] theelectron localization function, and the one-electron potential. [8] Furthermore,t he energy den-

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Testing the tools for revealing and characterizing the iodine–iodine halogen bond in crystals

Cited by 47 publications

References 69 publications

Noncovalent Bonds, Spectral and Thermal Properties of Substituted Thiazolo[2,3-b][1,3]thiazinium Triiodides

Noncovalent Bonds, Spectral and Thermal Properties of Substituted Thiazolo[2,3-b][1,3]thiazinium Triiodides

Pressure‐Induced Polymerization and Electrical Conductivity of a Polyiodide

Pressure‐Induced Polymerization and Electrical Conductivity of a Polyiodide

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