A Halogen‐Bonding Bis‐triazolium Rotaxane for Halide‐Selective Anion Recognition

Mullaney, Benjamin R.; Partridge, Benjamin E.; Beer, Paul D.

doi:10.1002/chem.201405578

Cited by 34 publications

(32 citation statements)

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[19] The 4,5 CH donors have been overlooked in receptor design,t hough they have not been without note. Li and co-workers [20] and then Beer and co-workers [21] investigated pincers that employed carbazoles as spacers to investigate the anion binding of amide-triazole and then halotriazolium binding sites, respectively.T he shifts in the 1 HNMR spectrum of the carbazole CH protons in response to anions gave motivation for us to investigate, for the first time, their ability to programt he inner spaces of macrocycles toward anions. If any anion bindingb ehavior was present,i tw ould also contribute to broadening the scope of examples [12, 22a-e] of neutralC H groups that are capable of engaging anions by Hb onding.…”

Section: Introductionmentioning

confidence: 99%

Multifunctional Tricarbazolo Triazolophane Macrocycles: One‐Pot Preparation, Anion Binding, and Hierarchical Self‐Organization of Multilayers

Lee

Hirsch

Liu

et al. 2015

Chemistry A European J

128

View full text Add to dashboard Cite

Programming the synthesis and self-assembly of molecules is a compelling strategy for the bottom-up fabrication of ordered materials. To this end, shape-persistent macrocycles were designed with alternating carbazoles and triazoles to program a one-pot synthesis and to bind large anions. The macrocycles bind anions that were once considered too weak to be coordinated, such as PF6 (-) , with surprisingly high affinities (β2 =10(11) M(-2) in 80:20 chloroform/methanol) and positive cooperativity, α=(4 K2 /K1 )=1200. We also discovered that the macrocycles assemble into ultrathin films of hierarchically ordered tubes on graphite surfaces. The remarkable surface-templated self-assembly properties, as was observed by using scanning tunneling microscopy, are attributed to the complementary pairing of alternating triazoles and carbazoles inscribed into both the co-facial and edge-sharing seams that exist between shape-persistent macrocycles. The multilayer assembly is also consistent with the high degree of molecular self-association observed in solution, with self-association constants of K=300 000 M(-1) (chloroform/methanol 80:20). Scanning tunneling microscopy data also showed that surface assemblies readily sequester iodide anions from solution, modulating their assembly. This multifunctional macrocycle provides a foundation for materials composed of hierarchically organized and nanotubular self-assemblies.

show abstract

Section: Introductionmentioning

confidence: 99%

Multifunctional Tricarbazolo Triazolophane Macrocycles: One‐Pot Preparation, Anion Binding, and Hierarchical Self‐Organization of Multilayers

Lee

Hirsch

Liu

et al. 2015

Chemistry A European J

128

View full text Add to dashboard Cite

show abstract

“…Furthermore, rotaxane interlocked host structural frameworks containing convergent XB triazolium donor groups have been demonstrated to selectively recognize and sense halide anions in highly competitive aqueous media. 59 , 61 , 62 …”

Section: Introductionmentioning

confidence: 99%

Evidence for Halogen Bond Covalency in Acyclic and Interlocked Halogen-Bonding Receptor Anion Recognition

et al. 2014

Self Cite

View full text Add to dashboard Cite

The synthesis and anion binding properties of novel halogen-bonding (XB) bis-iodotriazole-pyridinium-containing acyclic and [2]catenane anion host systems are described. The XB acyclic receptor displays selectivity for acetate over halides with enhanced anion recognition properties compared to the analogous hydrogen-bonding (HB) acyclic receptor. A reversal in halide selectivity is observed in the XB [2]catenane, in comparison to the acyclic XB receptor, due to the interlocked host’s unique three-dimensional binding cavity, and no binding is observed for oxoanions. Notable halide anion association constant values determined for the [2]catenane in competitive organic–aqueous solvent mixtures demonstrate considerable enhancement of anion recognition as compared to the HB catenane analogue. X-ray crystallographic analysis of a series of halide catenane complexes reveal strong XB interactions in the solid state. These interactions were studied using Cl and Br K-edge X-ray Absorption Spectroscopy (XAS) indicating intense pre-edge features characteristic of charge transfer from the halide to its bonding partner (σAX←X–* ← X1s), and providing a direct measure of the degree of covalency in the halogen bond(s). The data reveal that the degree of covalency is similar to that which is observed in transition metal coordinate covalent bonds. These results are supported by DFT results, which correlate well with the experimental data.

show abstract

“…All these interactions have recentlyb een widely explored in the fields of crystallography, [26] supramolecular chemistry, [27,28] biochemistry, [29,30] and catalysis, [31][32][33] just to name af ew.H owever,w ew ere particularly interested in another field, hole interactions as receptors [34] of halides. [35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54] In ar ecent article, Scheiner [55] proposedadithieno-thiophenef ramework (1 Y ,s ee Figure 1) to create selectiveh alide receptors. By replacing the upper sulfur atoms with germanium atoms, strong s holes and correspondinglys trong tetrel bonds are formed with halides.…”

Section: S-hole Interactionsmentioning

confidence: 99%

Ping‐Pong Tunneling Reactions: Can Fluoride Jump at Absolute Zero?

Nandi

Sucher

Kozuch

2018

Chemistry A European J

View full text Add to dashboard Cite

In a recent study, Scheiner designed a double-germanium-based fluoride receptor that binds the halogen by means of strong tetrel bonds (Chem. Eur. J. 2016, 22, 18850). In this system the F binds to the germanium atoms in an asymmetric fashion, thereby producing a double-well potential in which the fluoride can jump from one germanium to the other as in a ping-pong game. Herein we prove through the use of computational tools that at cryogenic temperatures this rearrangement occurs by heavy-atom quantum mechanical tunneling. The inductive strength of the substituents and the polarity of the solvent can modify the barrier and the tunneling rate. But the strongest effect is observed upon modification of the geometry of the molecule by specific substitutions that affect the barrier width, the most critical factor in a tunneling mechanism. We postulate two experimental tests, one by microwave spectroscopy and one by cryogenic NMR spectroscopy, that can prove the predicted fluoride tunneling.

show abstract

A Halogen‐Bonding Bis‐triazolium Rotaxane for Halide‐Selective Anion Recognition

Cited by 34 publications

References 65 publications

Multifunctional Tricarbazolo Triazolophane Macrocycles: One‐Pot Preparation, Anion Binding, and Hierarchical Self‐Organization of Multilayers

Multifunctional Tricarbazolo Triazolophane Macrocycles: One‐Pot Preparation, Anion Binding, and Hierarchical Self‐Organization of Multilayers

Evidence for Halogen Bond Covalency in Acyclic and Interlocked Halogen-Bonding Receptor Anion Recognition

Ping‐Pong Tunneling Reactions: Can Fluoride Jump at Absolute Zero?

Contact Info

Product

Resources

About