Self-Assembly of Complementary Components Using a Tripodal Bismuth Compound: Pnictogen Bonding or Coordination Chemistry?

Moaven, Shiva; Watson, Brandon; Polaske, Thomas J; Karl, B.; Unruh, Daniel K.; Bowling, Nathan P.; Cozzolino, Anthony F.

doi:10.1021/acs.inorgchem.1c01232

Cited by 9 publications

(13 citation statements)

References 53 publications

(88 reference statements)

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“…Sb and Bi are used as an efficient pnicogen bonding donors for formation of supramolecular architectures in solution, solid state, catalysis, etc. [75][76][77]. In this context, the propensity of nitrogen, being the third most electronegative element with its extremely low polarizability, to act as a pnicogen bond donor remains questionable.…”

Section: Carbon Bonding Pnicogen Bonding and Hydrophobic Interactionsmentioning

confidence: 99%

The Relevance of Experimental Charge Density Analysis in Unraveling Noncovalent Interactions in Molecular Crystals

et al. 2022

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The work carried out by our research group over the last couple of decades in the context of quantitative crystal engineering involves the analysis of intermolecular interactions such as carbon (tetrel) bonding, pnicogen bonding, chalcogen bonding, and halogen bonding using experimental charge density methodology is reviewed. The focus is to extract electron density distribution in the intermolecular space and to obtain guidelines to evaluate the strength and directionality of such interactions towards the design of molecular crystals with desired properties. Following the early studies on halogen bonding interactions, several “sigma-hole” interaction types with similar electrostatic origins have been explored in recent times for their strength, origin, and structural consequences. These include interactions such as carbon (tetrel) bonding, pnicogen bonding, chalcogen bonding, and halogen bonding. Experimental X-ray charge density analysis has proved to be a powerful tool in unraveling the strength and electronic origin of such interactions, providing insights beyond the theoretical estimates from gas-phase molecular dimer calculations. In this mini-review, we outline some selected contributions from the X-ray charge density studies to the field of non-covalent interactions (NCIs) involving elements of the groups 14–17 of the periodic table. Quantitative insights into the nature of these interactions obtained from the experimental electron density distribution and subsequent topological analysis by the quantum theory of atoms in molecules (QTAIM) have been discussed. A few notable examples of weak interactions have been presented in terms of their experimental charge density features. These examples reveal not only the strength and beauty of X-ray charge density multipole modeling as an advanced structural chemistry tool but also its utility in providing experimental benchmarks for the theoretical studies of weak interactions in crystals.

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Section: Carbon Bonding Pnicogen Bonding and Hydrophobic Interactionsmentioning

confidence: 99%

The Relevance of Experimental Charge Density Analysis in Unraveling Noncovalent Interactions in Molecular Crystals

et al. 2022

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“…It is commonly held that the three σ-holes generated around a PnX 3 molecule would be conducive to the formation of up to three PnBs [ 97 , 98 ]. For example, the Cozzolino group [ 99 ] identified three such bonds in the internal geometry of Bi((NC 9 H 7 ) 3 CH 3 ) that persist in solution. A detailed examination of this question [ 100 ] provided a nuanced answer in the general case.…”

Section: Discussionmentioning

confidence: 99%

Involvement of Arsenic Atom of AsF3 in Five Pnicogen Bonds: Differences between X-ray Structure and Theoretical Models

2022

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Bonding within the AsF3 crystal is analyzed via quantum chemical methods so as to identify and quantify the pnicogen bonds that are present. The structure of a finite crystal segment containing nine molecules is compared with that of a fully optimized cluster of the same size. The geometries are qualitatively different, with a much larger binding energy within the optimized nonamer. Although the total interaction energy of a central unit with the remaining peripheral molecules is comparable for the two structures, the binding of the peripherals with one another is far larger in the optimized cluster. This distinction of much stronger total binding within the optimized cluster is not limited to the nonamer but repeats itself for smaller aggregates as well. The average binding energy of the cluster rises quickly with size, asymptotically approaching a value nearly triple that of the dimer.

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“…According to the molecular electrostatic potential mapping of BiAz, as drawn in Figure S17, it was shown that BiAz could have a positive potential on hypervalent bismuth. 19 The area of the positive potential in BiAz is more expansive than that in TAz (Figure S17). These results imply that the effective Lewis acidity of hypervalent bismuth might be stronger than that of hypervalent tin.…”

Section: Nmr Spectroscopic Analysismentioning

confidence: 99%

Effects of Hypervalent Bismuth on Electronic Properties of the Azobenzene Tridentate Ligand and Roles of Lewis Acidity in Controlling Optical Properties

2023

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Organobismuth compounds have been studied in various fields, including electronic states, pnictogen bonds, and catalysis. Among them, one of the unique electronic states of the element is the hypervalent state. So far, many issues regarding the electronic structures of bismuth in hypervalent states have been revealed; meanwhile, the influence of hypervalent bismuth on the electronic properties of π-conjugated scaffolds is still vailed. Here, we synthesized the hypervalent bismuth compound, BiAz, by introducing hypervalent bismuth into the azobenzene tridentate ligand as a π-conjugated scaffold. The influence of hypervalent bismuth on the electronic properties of the ligand was evaluated from optical measurements and quantum chemical calculations. The introduction of hypervalent bismuth revealed three significant electronic effects: first, hypervalent bismuth shows position-dependent electron-donating and electron-accepting effects. Second, BiAz can have a larger effective Lewis acidity than the hypervalent tin compound derivatives reported in our previous research. Finally, the coordination of dimethyl sulfoxide transformed the electronic properties of BiAz, similar to the hypervalent tin compounds. The data from quantum chemical calculations showed that the optical properties of the π-conjugated scaffold were able to be changed by introducing hypervalent bismuth. To the best of our knowledge, we first demonstrate that the introduction of hypervalent bismuth should be a new methodology for controlling the electronic properties of π-conjugated molecules and developing sensing materials.

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Self-Assembly of Complementary Components Using a Tripodal Bismuth Compound: Pnictogen Bonding or Coordination Chemistry?

Cited by 9 publications

References 53 publications

The Relevance of Experimental Charge Density Analysis in Unraveling Noncovalent Interactions in Molecular Crystals

The Relevance of Experimental Charge Density Analysis in Unraveling Noncovalent Interactions in Molecular Crystals

Involvement of Arsenic Atom of AsF3 in Five Pnicogen Bonds: Differences between X-ray Structure and Theoretical Models

Effects of Hypervalent Bismuth on Electronic Properties of the Azobenzene Tridentate Ligand and Roles of Lewis Acidity in Controlling Optical Properties

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