How Do Distance and Solvent Affect Halogen Bonding Involving Negatively Charged Donors?

Chen, Zhaoqiang; Wang, Guimin; Xu, Zhijian; Wang, Jinan; Yu, Yuqi; Cai, Tingting; Shao, Qiang; Shi, Jiye; Zhu, Weiliang

doi:10.1021/acs.jpcb.6b05027

Cited by 20 publications

(27 citation statements)

References 73 publications

(107 reference statements)

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“…Other types of relateds ystems forw hich it has found good successi nclude HBs, [89][90][91][92][93][94][95] both neutral, and those involving an anion, [96] especially pertinent here. M06-2X appears to do very well in pnicogen and chalcogen bonded systems [106,107] of particularr elevance here, even those containing an ion [108,109] as do the systems examined here. [97][98][99][100][101][102][103] Ones tudy, for example, found M06-2X stacked up well against CCSD(T) data with ac omplete basis set, [104] superior to all other DFT methods examined.…”

Section: Discussionmentioning

confidence: 54%

“…Another also found that this functional yielded results in good agreement with CCSD(T). M06‐2X appears to do very well in pnicogen and chalcogen bonded systems of particular relevance here, even those containing an ion as do the systems examined here. One work in particular found M06‐2X quite accurate when considering a tripodal perhalophenyl halogen‐bonding system.…”

Section: Discussionmentioning

confidence: 65%

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Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Scheiner

2016

Chemistry A European J

101

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The interactions of halides with a number of bipodal receptors were examined by quantum chemical methods. The receptors were based on a dithieno thiophene framework in which two S atoms can engage in a pair of chalcogen bonds with a halide. These two S atoms were replaced by P and As atoms to compare chalcogen with pnicogen bonding, and by Ge which engages in tetrel bonds with the receptor. Zero, one, and two O atoms were added to the thiophene S atom which is not directly involved in the interaction with the halides. Fluoride bound the most strongly, followed by Cl , Br , and I , respectively. Replacing S by the pnicogen bonds of P strengthened the binding, as did moving down to As in the third row of the periodic table. A further large increment is associated with the switch to the tetrel bonds of Ge. Even though the thiophene S atom is remote from the binding site, each additional O atom added to it raises the binding energy, which can be quite large, as much as 63 kcal mol for the Ge⋅⋅⋅F interaction. The receptors have a pronounced selectivity for F over the other halides, as high as 27 orders of magnitude. The data suggest that incorporation of tetrel atoms may lead to new and more powerful halide receptors.

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Section: Discussionmentioning

confidence: 54%

Section: Discussionmentioning

confidence: 65%

Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Scheiner

2016

Chemistry A European J

101

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“…There seems to be no universal dependence which can be used to estimate the halogen bond energy using the interatomic distances and bond angles. The previously reported correlations were tested on relatively homologous sets of intermolecular complexes [47,68]. Here, using our set of 128 complexes with participation of various halogens, we attempt to construct energy-structure correlations which on one hand would be general enough (i.e., would have similar form for all halogen donor types) and on the other hand would be simple enough, allowing for a rapid energy estimation.…”

Section: Complexation Energy Dependence On Intermolecular Distancementioning

confidence: 99%

Phosphine Oxides as Spectroscopic Halogen Bond Descriptors: IR and NMR Correlations with Interatomic Distances and Complexation Energy

et al. 2020

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An extensive series of 128 halogen-bonded complexes formed by trimethylphosphine oxide and various F-, Cl-, Br-, I- and At-containing molecules, ranging in energy from 0 to 124 kJ/mol, is studied by DFT calculations in vacuum. The results reveal correlations between R–X⋅⋅⋅O=PMe3 halogen bond energy ΔE, X⋅⋅⋅O distance r, halogen’s σ-hole size, QTAIM parameters at halogen bond critical point and changes of spectroscopic parameters of phosphine oxide upon complexation, such as 31P NMR chemical shift, ΔδP, and P=O stretching frequency, Δν. Some of the correlations are halogen-specific, i.e., different for F, Cl, Br, I and At, such as ΔE(r), while others are general, i.e., fulfilled for the whole set of complexes at once, such as ΔE(ΔδP). The proposed correlations could be used to estimate the halogen bond properties in disordered media (liquids, solutions, polymers, glasses) from the corresponding NMR and IR spectra.

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“…The Gaussian-09 [77] program (Gaussian Inc., Wallingford, CT, USA) was employed for all calculations which were carried out with the M06-2X DFT functional, which has shown itself to be reliable and accurate for related systems [78,79,80,81,82,83,84]. The aug-cc-pVDZ basis set was used for all atoms, with the exception of Sn, for which the aug-cc-pVDZ-PP pseudopotential from the EMSL library [85,86] was applied so as to account for relativistic effects.…”

Section: Methodsmentioning

confidence: 99%

Differential Binding of Tetrel-Bonding Bipodal Receptors to Monatomic and Polyatomic Anions

Scheiner

2019

Molecules

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Previous work has demonstrated that a bidentate receptor containing a pair of Sn atoms can engage in very strong interactions with halide ions via tetrel bonds. The question that is addressed here concerns the possibility that a receptor of this type might be designed that would preferentially bind a polyatomic over a monatomic anion since the former might better span the distance between the two Sn atoms. The binding of Cl− was thus compared to that of HCOO−, HSO4−, and H2PO4− with a wide variety of bidentate receptors. A pair of SnFH2 groups, as strong tetrel-binding agents, were first added to a phenyl ring in ortho, meta, and para arrangements. These same groups were also added in 1,3 and 1,4 positions of an aliphatic cyclohexyl ring. The tetrel-bonding groups were placed at the termini of (-C≡C-)n (n = 1,2) extending arms so as to further separate the two Sn atoms. Finally, the Sn atoms were incorporated directly into an eight-membered ring, rather than as appendages. The ordering of the binding energetics follows the HCO2− > Cl− > H2PO4− > HSO4− general pattern, with some variations in selected systems. The tetrel bonding is strong enough that in most cases, it engenders internal deformations within the receptors that allow them to engage in bidentate bonding, even for the monatomic chloride, which mutes any effects of a long Sn···Sn distance within the receptor.

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How Do Distance and Solvent Affect Halogen Bonding Involving Negatively Charged Donors?

Cited by 20 publications

References 73 publications

Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Phosphine Oxides as Spectroscopic Halogen Bond Descriptors: IR and NMR Correlations with Interatomic Distances and Complexation Energy

Differential Binding of Tetrel-Bonding Bipodal Receptors to Monatomic and Polyatomic Anions

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