Triple-Pnictogen Bonding as a Tool for Supramolecular Assembly

Moaven, Shiva; Andrews, Miranda C.; Polaske, Thomas J; Karl, B.; Unruh, Daniel K.; Bosch, Eric; Bowling, Nathan P.; Cozzolino, Anthony F.

doi:10.1021/acs.inorgchem.9b02761

Cited by 44 publications

(56 citation statements)

References 59 publications

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“…As mentioned above, these two elements undertake stronger PnBs than N and P. Precisely, their use in supramolecular catalysis [94,95] and anion recognition [96] has been recently demonstrated. Among the heavier pnictogens, antimony is the most promising pnictogen atom to be used in supramolecular chemistry and, particularly, for the recognition of anions.…”

Section: Arsenic and Antimonymentioning

confidence: 93%

On the Importance of σ–Hole Interactions in Crystal Structures

Frontera

Bauzá

2021

Crystals

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Elements from groups 14–18 and periods 3–6 commonly behave as Lewis acids, which are involved in directional noncovalent interactions (NCI) with electron-rich species (lone pair donors), π systems (aromatic rings, triple and double bonds) as well as nonnucleophilic anions (BF4−, PF6−, ClO4−, etc.). Moreover, elements of groups 15 to 17 are also able to act as Lewis bases (from one to three available lone pairs, respectively), thus presenting a dual character. These emerging NCIs where the main group element behaves as Lewis base, belong to the σ–hole family of interactions. Particularly (i) tetrel bonding for elements belonging to group 14, (ii) pnictogen bonding for group 15, (iii) chalcogen bonding for group 16, (iv) halogen bonding for group 17, and (v) noble gas bondings for group 18. In general, σ–hole interactions exhibit different features when moving along the same group (offering larger and more positive σ–holes) or the same row (presenting a different number of available σ–holes and directionality) of the periodic table. This is illustrated in this review by using several examples retrieved from the Cambridge Structural Database (CSD), especially focused on σ–hole interactions, complemented with molecular electrostatic potential surfaces of model systems.

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Section: Arsenic and Antimonymentioning

confidence: 93%

On the Importance of σ–Hole Interactions in Crystal Structures

Frontera

Bauzá

2021

Crystals

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“…P•••π and π-hole pnictogen bonds have been studied [159,160] and the Cl3P•••C6H6 complex studied experimentally by FTIR spectroscopy (Figure 11) [159]. Two important papers have been published, one on the catalysis by pnictogen bonds where there is a distinction between PH2F σ-hole vs. PO2F π-hole [161], and the other of supramolecular structures using triple pnictogen bonds [162]. One of our main contributions to pnictogen bonds are the EOM/CCSD calculations, made by J. E. Del Bene, of 31 P coupling constants through the pnictogen bond, we called np J(X-31 P) [142].…”

Section: Pnictogen Bondsmentioning

confidence: 99%

Not Only Hydrogen Bonds: Other Noncovalent Interactions

2020

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In this review, we provide a consistent description of noncovalent interactions, covering most groups of the Periodic Table. Different types of bonds are discussed using their trivial names. Moreover, the new name “Spodium bonds” is proposed for group 12 since noncovalent interactions involving this group of elements as electron acceptors have not yet been named. Excluding hydrogen bonds, the following noncovalent interactions will be discussed: alkali, alkaline earth, regium, spodium, triel, tetrel, pnictogen, chalcogen, halogen, and aerogen, which almost covers the Periodic Table entirely. Other interactions, such as orthogonal interactions and π-π stacking, will also be considered. Research and applications of σ-hole and π-hole interactions involving the p-block element is growing exponentially. The important applications include supramolecular chemistry, crystal engineering, catalysis, enzymatic chemistry molecular machines, membrane ion transport, etc. Despite the fact that this review is not intended to be comprehensive, a number of representative works for each type of interaction is provided. The possibility of modeling the dissociation energies of the complexes using different models (HSAB, ECW, Alkorta-Legon) was analyzed. Finally, the extension of Cahn-Ingold-Prelog priority rules to noncovalent is proposed.

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“…[1] The uniquef eature of the pnictogen atom comparedt o halogen and chalcogen, is the possibility to form three pnictogen bonds, providinga dditional opportunities for the crystal engineering. [11,25,26] Antimony(III) halidesa nd organoantinomy derivativesa re classical amphoteric compounds, which find broad application in the coordination chemistry.T hese compounds utilize the lone pairs on Sb or halogena toms to act as Lewisb ases towards the transition metals and the main group elements. [27][28][29][30][31] Sb III can also accept the lone pairo fadonor ligand, acting as the Lewis acid.…”

Section: Introductionmentioning

confidence: 99%

“…conclude that such individual atom‐atom pair interactions (of atoms in a crystal) are structure determining [1] . The unique feature of the pnictogen atom compared to halogen and chalcogen, is the possibility to form three pnictogen bonds, providing additional opportunities for the crystal engineering [11, 25, 26] …”

Section: Introductionmentioning

confidence: 99%

Structures and Chemical Bonding in Antimony(III) Bromide Complexes with Pyridine

Prokudina

Davydova

Вировец

et al. 2020

Chemistry A European J

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Weakly or "partially" bondedm oleculesa re an importantl ink between the chemical and van der Waals interactions. Molecular structures of sixn ew SbBr 3-Py complexes in the solid state have been determined by single-crystal Xray diffraction analysis. In all complexesa ll Sb atoms adopt a pseudo-octahedral coordinationg eometry whichi sc ompleted by additional Sb•••Brc ontacts shorter than the sum of the van der Waals radii, with BrÀSb•••Br angles close to 1808.T o reveal the nature of Sb-Br and Sb-N interactions, the DFT calculations were performedf ollowed by the analysis of the electrostatic potentials, the orbital interactions and the topological analysis.B ased on Natural Bond Orbital (NBO) analysis, the Sb-Bri nteractionsr ange from the covalent bonds to the pnictogenb onds. As imple structural parameter, non-covalence criterion (NCC) is defined as ar atio of the atomatom distance to the linear combination of sums of covalent and van der Waals radii. NCC correlates with E(2) values for SbÀN, SbÀCl and SbÀBr bonds, and appearst ob eu seful criterion for ap reliminary evaluation of the bonding situation.

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Triple-Pnictogen Bonding as a Tool for Supramolecular Assembly

Cited by 44 publications

References 59 publications

On the Importance of σ–Hole Interactions in Crystal Structures

On the Importance of σ–Hole Interactions in Crystal Structures

Not Only Hydrogen Bonds: Other Noncovalent Interactions

Structures and Chemical Bonding in Antimony(III) Bromide Complexes with Pyridine

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