Chalcogen-bond driven molecular recognition at work

Biot, Nicolas; Bonifazi, Davide

doi:10.1016/j.ccr.2020.213243

Cited by 219 publications

(198 citation statements)

References 132 publications

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“…UV-vis titration experiments carried out in MeCN by addition of TBACl indicate that the dications ([3] 2+ and [4] 2+ ) display chloride binding constants in excess of 10 6 M À1 , in agreement with the high V S,max values dening their antimony-centred s-hole. The optimized structures of the corresponding chloride complexes suggest that the chloride anion is concomitantly stabilized via pnictogenbonding at the stibonium center and chalcogen-bonding [43][44][45][46][47][48][49][50] at the sulfonium center (Scheme 2). 35,37,51 The monocations […”

Section: Resultsmentioning

confidence: 99%

Redox-controlled chalcogen and pnictogen bonding: the case of a sulfonium/stibonium dication as a preanionophore for chloride anion transport

Park

Gabbaı̈

2020

Chem. Sci.

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Section: Resultsmentioning

confidence: 99%

Redox-controlled chalcogen and pnictogen bonding: the case of a sulfonium/stibonium dication as a preanionophore for chloride anion transport

Park

Gabbaı̈

2020

Chem. Sci.

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“…13 C NMR spectrum of 2-MeTfO, Figure S9. 19 F NMR spectrum of 2-MeTfO, Figure S10. 1 H NMR spectrum of 4-MeTfO, Figure S11.…”

Section: Uv-vis Spectramentioning

confidence: 99%

“…Chalcogen bonds (ChBs) result from interaction between an electrophilic region of a Group VI element (i.e., S, Se, Te) and a Lewis base. Due to their strength and directionality (comparable to hydrogen and halogen bonds) ChBs are intriguing alternatives to the predominant hydrogen bonding in various areas of research including crystal engineering, organic reactivity and catalysis [16,17], as well as anion transport and recognition [13,18,19].…”

Section: Introductionmentioning

confidence: 99%

Effect of Aromatic System Expansion on Crystal Structures of 1,2,5-Thia- and 1,2,5-Selenadiazoles and Their Quaternary Salts: Synthesis, Structure, and Spectroscopic Properties

et al. 2020

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Rational manipulation of secondary bonding interactions is a crucial factor in the construction of new chalcogenadiazole-based materials. This article reports detailed experimental studies on phenanthro[9,10-c][1,2,5]chalcogenadiazolium and 2,1,3-benzochalcogenadiazolium salts and their precursors. The compounds were synthesized, characterized employing NMR and UV-Vis spectroscopy. TD-DFT calculations were also performed. The influence of the size of the aromatic system on the molecular motifs formed by the compounds in the solid state has been studied by means of single-crystal X-ray diffraction. In case of the salts, the nature of an anion was also taken into consideration. The results show that cyclic [E···N]2 supramolecular synthon connects neighboring molecules of phenanthro[9,10-c][1,2,5]chalcogenadiazoles, with a relatively large aromatic system, in dimers regardless of the chalcogen atom in the molecule. Both N-methyl-2,1,3-benzothiadiazolium and N-methylphenanthro[9,10-c][1,2,5]chalcogenadiazolium cations have a strong affinity for triflate and iodide anions, therefore the formation of S···N or Se···N secondary bonding interactions is observed only in two out of the eight quaternary salts. Less coordinating anions must be used to enable the building blocks studied to form cyclic [E···N]2 synthons. Moreover, for two of the triflate salts, which are isostructural, a new supramolecular motif has been observed.

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“…Several studies have proven that computing V associated with a σ-hole in its unperturbed state can furnish a useful estimation of the strength of potential noncovalent interactions involving the electropositive region [ 2 , 5 ]. Among noncovalent interactions related to the σ-hole concept, the well-known halogen [ 8 ] and chalcogen [ 9 ] bonds (XB and ChB, respectively) have been studied and applied in several fields for decades [ 10 , 11 , 12 , 13 ]. Because V in a region depends on the contributions of the whole molecule [ 14 , 15 ], seminal studies have focused on the structural factors which affect local V by using simple compounds as test probes [ 14 , 16 , 17 , 18 ].…”

Section: Introductionmentioning

confidence: 99%

Factors Impacting σ- and π-Hole Regions as Revealed by the Electrostatic Potential and Its Source Function Reconstruction: The Case of 4,4′-Bipyridine Derivatives

Gatti¹,

Dessì

Dallocchio

et al. 2020

Molecules

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Positive electrostatic potential (V) values are often associated with σ- and π-holes, regions of lower electron density which can interact with electron-rich sites to form noncovalent interactions. Factors impacting σ- and π-holes may thus be monitored in terms of the shape and values of the resulting V. Further precious insights into such factors are obtained through a rigorous decomposition of the V values in atomic or atomic group contributions, a task here achieved by extending the Bader–Gatti source function (SF) for the electron density to V. In this article, this general methodology is applied to a series of 4,4′-bipyridine derivatives containing atoms from Groups VI (S, Se) and VII (Cl, Br), and the pentafluorophenyl group acting as a π-hole. As these molecules are characterized by a certain degree of conformational freedom due to the possibility of rotation around the two C–Ch bonds, from two to four conformational motifs could be identified for each structure through conformational search. On this basis, the impact of chemical and conformational features on σ- and π-hole regions could be systematically evaluated by computing the V values on electron density isosurfaces (VS) and by comparing and dissecting in atomic/atomic group contributions the VS maxima (VS,max) values calculated for different molecular patterns. The results of this study confirm that both chemical and conformational features may seriously impact σ- and π-hole regions and provide a clear analysis and a rationale of why and how this influence is realized. Hence, the proposed methodology might offer precious clues for designing changes in the σ- and π-hole regions, aimed at affecting their potential involvement in noncovalent interactions in a desired way.

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Chalcogen-bond driven molecular recognition at work

Abstract: and the EU through the MSCA-RISE funding scheme (project INFUSION) for the financial support.

Cited by 219 publications

References 132 publications

Redox-controlled chalcogen and pnictogen bonding: the case of a sulfonium/stibonium dication as a preanionophore for chloride anion transport

Redox-controlled chalcogen and pnictogen bonding: the case of a sulfonium/stibonium dication as a preanionophore for chloride anion transport

Effect of Aromatic System Expansion on Crystal Structures of 1,2,5-Thia- and 1,2,5-Selenadiazoles and Their Quaternary Salts: Synthesis, Structure, and Spectroscopic Properties

Factors Impacting σ- and π-Hole Regions as Revealed by the Electrostatic Potential and Its Source Function Reconstruction: The Case of 4,4′-Bipyridine Derivatives

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