Geometrical and energetic characteristics of Se⋯Se interactions in crystal structures of organoselenium molecules

Veljković, Ivana; Kretić, Danijela S.; Veljković, Dušan Ž.

doi:10.1039/d1ce00129a

Cited by 2 publications

(3 citation statements)

References 46 publications

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“…Nevertheless, selenophene-based PBTSDPP exhibits a much larger L π of 38.51 Å than thiophene-based PBTTDPP with an L π of 18.01 Å, which can be attributed to the stronger Se−Se or Se−π interactions induced by the BTS units in PBTSDPP. 72,73 Larger L π from PBTSDPP yields a smaller R L , which leads to favorable edgeon orientation. Meanwhile, the smaller L π from PBTTDPP outputs a larger R L , favoring the formation of the face-on orientation.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis of Asymmetric Benzotrithiophene/Benzotriselenophene Building Blocks and Their Donor–Acceptor Copolymers: Chalcogen Effect on Face-on/Edge-on Orientations and Charge Transport

Huang,

Pao,

Chen

et al. 2023

Macromolecules

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Two asymmetric 5-octadecanyl benzotrithiophene (BTT) and benzotriselenophene (BTS) were designed and synthesized through a key step of palladium-catalyzed intramolecular C–H arylation. The two-dimensional stannylated BTT and BTS monomers were then polymerized with a DPP comonomer by Stille coupling to afford two new donor–acceptor polymers, PBTTDPP and PBTSDPP. With the chalcogen effect of selenium, PBTSDPP exhibited a higher-lying HOMO level and a more red-shifted absorption than the corresponding PBTTDPP. The crystalline domains of both PBTTDPP and PBTSDPP were analyzed via GIWAXS measurements, revealing perpendicular π–π stacking of the main-chain backbone and lamellar stacking of side-chain interdigitation. The dimensions of the π–π stacking and lamellar stacking of the crystalline domains were estimated by calculating their corresponding correlation lengths (L c). We discovered that the ratio between the correlation lengths of lamellar stacking (L l) and π–π stacking (L π), denoted as (R L), plays a crucial role in determining the edge-on/face-on polymer orientations of substrates. PBTTDPP, with a larger R L of 2.56, predominantly exhibits a face-on orientation, while PBTSDPP, which has a stronger π–π interaction due to Se inclusion, leads to a smaller R L of 1.36, preferring an edge-on orientation. After thermal annealing at 210 °C for 10 min, PBTSDPP forms higher-order crystalline domains, increasing its mobility from 0.04 to 0.17 cm2 V–1 s–1. Despite its face-on orientation, the pristine PBTTDPP, with a higher molecular weight, exhibits the best mobility of 0.61 cm2 V–1 s–1 due to efficient intrachain charge transport and good connectivity between different nanodomains. However, thermal annealing of PBTTDPP leads to a decrease in π–π stacking distance from 3.67 to 3.41 Å, facilitating charge transport via face-on π-stacking hopping perpendicular to the source-to-drain direction. Consequently, the mobility of annealed PBTTDPP is reduced to 0.18 cm2 V–1 s–1. This work demonstrates that the use of benzotrichalcogenophenes in the polymer backbone can fine-tune intermolecular interactions, controlling the orientations in crystalline nanodomains that ultimately determine the charge transport properties.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis of Asymmetric Benzotrithiophene/Benzotriselenophene Building Blocks and Their Donor–Acceptor Copolymers: Chalcogen Effect on Face-on/Edge-on Orientations and Charge Transport

Huang,

Pao,

Chen

et al. 2023

Macromolecules

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“…Currently, quantum chemical calculations and several spectroscopic techniques such as X-ray diffraction and NMR spectroscopy have been mainly used to investigate selenium-centered chalcogen bonds (SeChBs). These SeChBs mainly include Se ∙∙∙ N [ 47 , 48 , 49 , 50 , 51 , 52 ], Se ∙∙∙ O [ 10 , 13 , 47 , 51 , 53 , 54 ], Se ∙∙∙ S [ 47 , 55 ], Se ∙∙∙ Se [ 28 , 56 , 57 ], and Se ∙∙∙ π [ 58 , 59 , 60 ] contacts. Zhang [ 48 ], Mugesh [ 61 ], and Panda [ 11 ] and colleagues theoretically investigated the impacts of the substituents covalently bonded to the Se atom, hybridization of the nitrogen atom, the chelate ring, and rigidity on Se ∙∙∙ N ChBs.…”

Section: Introductionmentioning

confidence: 99%

“…Bauzá and colleagues [ 55 ] also demonstrated the significance of intermolecular Se ∙∙∙ O/S ChBs in the stabilization of protein–ligand complexes involving Se–pyranose through PDB surveys. Veljković et al [ 57 ] conducted a statistical analysis of crystallographic data from the Cambridge Structural Database (CSD), revealing the cooperative roles of Se ∙∙∙ Se ChBs and C/Se–H ∙∙∙ Se HBs in stabilizing crystal structures of organoselenium compounds. Tskhovrebov and coworkers [ 59 ] reported that symmetrical dimers of benzylic-substituted 1,2,4-selenodiazolium salts are stabilized through Se ∙∙∙ N and Se ∙∙∙ π ChBs, where the former are weaker than the latter.…”

Section: Introductionmentioning

confidence: 99%

Unveiling the Nature and Strength of Selenium-Centered Chalcogen Bonds in Binary Complexes of SeO2 with Oxygen-/Sulfur-Containing Lewis Bases: Insights from Theoretical Calculations

Lu,

Chen,

Liu

et al. 2024

IJMS

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Among various non-covalent interactions, selenium-centered chalcogen bonds (SeChBs) have garnered considerable attention in recent years as a result of their important contributions to crystal engineering, organocatalysis, molecular recognition, materials science, and biological systems. Herein, we systematically investigated π–hole-type Se∙∙∙O/S ChBs in the binary complexes of SeO2 with a series of O-/S-containing Lewis bases by means of high-level ab initio computations. The results demonstrate that there exists an attractive interaction between the Se atom of SeO2 and the O/S atom of Lewis bases. The interaction energies computed at the MP2/aug-cc-pVTZ level range from −4.68 kcal/mol to −10.83 kcal/mol for the Se∙∙∙O chalcogen-bonded complexes and vary between −3.53 kcal/mol and −13.77 kcal/mol for the Se∙∙∙S chalcogen-bonded complexes. The Se∙∙∙O/S ChBs exhibit a relatively short binding distance in comparison to the sum of the van der Waals radii of two chalcogen atoms. The Se∙∙∙O/S ChBs in all of the studied complexes show significant strength and a closed-shell nature, with a partially covalent character in most cases. Furthermore, the strength of these Se∙∙∙O/S ChBs generally surpasses that of the C/O–H∙∙∙O hydrogen bonds within the same complex. It should be noted that additional C/O–H∙∙∙O interactions have a large effect on the geometric structures and strength of Se∙∙∙O/S ChBs. Two subunits are connected together mainly via the orbital interaction between the lone pair of O/S atoms in the Lewis bases and the BD*(OSe) anti-bonding orbital of SeO2, except for the SeO2∙∙∙HCSOH complex. The electrostatic component emerges as the largest attractive contributor for stabilizing the examined complexes, with significant contributions from induction and dispersion components as well.

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Geometrical and energetic characteristics of Se⋯Se interactions in crystal structures of organoselenium molecules

Abstract: Non-covalent selenium-selenium interactions between selenium-containing organic molecules were studied in crystal structures from the Cambridge Structural Database and by high-level quantum chemical calculations. Se…Se contacts in crystal structures were analyzed...

Cited by 2 publications

References 46 publications

Synthesis of Asymmetric Benzotrithiophene/Benzotriselenophene Building Blocks and Their Donor–Acceptor Copolymers: Chalcogen Effect on Face-on/Edge-on Orientations and Charge Transport

Synthesis of Asymmetric Benzotrithiophene/Benzotriselenophene Building Blocks and Their Donor–Acceptor Copolymers: Chalcogen Effect on Face-on/Edge-on Orientations and Charge Transport

Unveiling the Nature and Strength of Selenium-Centered Chalcogen Bonds in Binary Complexes of SeO2 with Oxygen-/Sulfur-Containing Lewis Bases: Insights from Theoretical Calculations

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