Synthesis of Chiral Triazole-Based Halogen Bond Donors

Synthesis ◽  
2019 ◽  
Vol 51 (10) ◽  
pp. 2128-2135 ◽  
Author(s):  
Mikk Kaasik ◽  
Sandra Kaabel ◽  
Kadri Kriis ◽  
Ivar Järving ◽  
Tõnis Kanger
Keyword(s):  
Click Chemistry ◽  
Self Assembly ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Easy Access ◽  
Enantiomerically Pure ◽  
Wide Variability ◽  
Supramolecular Aggregation

The number of applications that use halogen bonding in the fields of self-assembly, supramolecular aggregation, and catalysis is growing. However, the accessibility of chiral halotriazoles shows that there is still a lot more to explore. The simple click-chemistry is applied for the straightforward synthesis of enantiomerically pure mono- and bidentate as well as multifunctional iodotriazole-based XB donors. The methodology is characterized by a wide variability due to easy access of chiral azides.

Cyclic networks of halogen-bonding interactions in molecular self-assemblies: a theoretical N—X...NversusC—X...N investigation

2017 ◽  
Vol 73 (2) ◽  
pp. 179-187
Author(s):  
Ruben D. Parra ◽  
Álvaro Castillo
Keyword(s):  
Electron Density ◽  
Self Assembly ◽  
Metal Ion ◽  
Halogen Atom ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Nbo Analysis ◽  
Binding Energies ◽  
Cyclic Network ◽  
Ability To Drive

The geometries and energetics of molecular self-assembly structures that contain a sequential network of cyclic halogen-bonding interactions are investigated theoretically. The strength of the halogen-bonding interactions is assessed by examining binding energies, electron charge transfer (NBO analysis) and electron density at halogen-bond critical points (AIM theory). Specifically, structural motifs having intramolecular N—X...N (X= Cl, Br, or I) interactions and the ability to drive molecular self-assemblyviathe same type of interactions are used to construct larger self-assemblies of up to three unit motifs. N—X...N halogen-bond cooperativity as a function of the self-assembly size, and the nature of the halogen atom is also examined. The cyclic network of the halogen-bonding interactions provides a suitable cavity rich in electron density (from the halogen atom lone pairs not involved in the halogen bonds) that can potentially bind an electron-deficient species such as a metal ion. This possibility is explored by examining the ability of the N—X...N network to bind Na+. Likewise, molecular self-assembly structures driven by the weaker C—X...N halogen-bonding interactions are investigated and the results compared with those of their N—X...N counterparts.

Tetradentate halogen bonding macrocyclic anion receptor inspired by the “Texas-sized” molecular box

2022 ◽  
Author(s):  
Tian Zhao ◽  
Vincent Lynch ◽  
Jonathan L. Sessler
Keyword(s):  
Click Chemistry ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Anion Receptor

Inspired by the tetracationic “Texas-sized” molecular box, a neutral analogue containing four iodotriazole halogen bond-promoting subunits (“Ibox”) was synthesized. This new macrocycle was prepared by means of azide-alkyne click chemistry....

scholarly journals One “Click” access to self-complementary molecular modules for halogen bonding

RSC Advances ◽  
2016 ◽  
Vol 6 (43) ◽  
pp. 36723-36727 ◽  
Author(s):  
G. Cavallo ◽  
P. Metrangolo ◽  
T. Pilati ◽  
G. Resnati ◽  
A. Scrivanti ◽  
...  
Keyword(s):  
Click Chemistry ◽  
Self Assembly ◽  
Halogen Bonding

The application of “click chemistry” has proved its efficacy for the construction of novel molecular modules for halogen bonding driven self-assembly.

scholarly journals A Raman Spectroscopic and Computational Study of New Aromatic Pyrimidine-Based Halogen Bond Acceptors

Inorganics ◽  
2019 ◽  
Vol 7 (10) ◽  
pp. 119 ◽  
Author(s):  
Hardin ◽  
Ellington ◽  
Nguyen ◽  
Rheingold ◽  
Tschumper ◽  
...  
Keyword(s):  
Self Assembly ◽  
Density Functional ◽  
Computational Study ◽  
Halogen Bond ◽  
Normal Modes ◽  
Halogen Bonding ◽  
Building Blocks ◽  
Molecular Assembly ◽  
X Ray ◽  
X Ray Crystallography

Two new aromatic pyrimidine-based derivatives designed specifically for halogen bond directed self-assembly are investigated through a combination of high-resolution Raman spectroscopy, X-ray crystallography, and computational quantum chemistry. The vibrational frequencies of these new molecular building blocks, pyrimidine capped with furan (PrmF) and thiophene (PrmT), are compared to those previously assigned for pyrimidine (Prm). The modifications affect only a select few of the normal modes of Prm, most noticeably its signature ring breathing mode, ν1. Structural analyses afforded by X-ray crystallography, and computed interaction energies from density functional theory computations indicate that, although weak hydrogen bonding (C–H···O or C–H···N interactions) is present in these pyrimidine-based solid-state co-crystals, halogen bonding and π-stacking interactions play more dominant roles in driving their molecular-assembly.

scholarly journals Porphyrin’s Ring Current as a Driving Force for Halogen Bond Interactions: A Computational Study

2019 ◽  
Author(s):  
Jyoti Rani ◽  
Hatem M. Titi ◽  
Ranjan Patra
Keyword(s):  
Self Assembly ◽  
Driving Force ◽  
Ring Current ◽  
Computational Study ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Porphyrin Ring

<p>We demonstrate herein a computational study probing the influence of metalloporphyrin ring current directionality on intermolecular halogen bonding (XB) during supramolecular self-assembly. The results demonstrate that porphyrin ring current can activate or deactivate halogen bonding interactions, an essential superamolecular driving force.</p>

Anion Templated Crystal Engineering of Halogen Bonding Tripodal Tris(halopyridinium) Compounds

2020 ◽  
Author(s):  
Emer Foyle ◽  
Nicholas White
Keyword(s):  
Crystal Engineering ◽  
Self Assembly ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Halogen Bonds ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Structural Database ◽  
Van Der Waals Radii

<div>In this work four new tripodal tris(halopyridinium) receptors containing potentially halogen</div><div>bonding groups were prepared. The ability of the receptors to bind anions in competitive</div><div>CD<sub>3</sub>CN/d<sub>6</sub>-DMSO was studied using <sup>1</sup>H NMR titration experiments, which revealed that the</div><div>receptors bind chloride anions more strongly than more basic acetate or other halide ions.</div><div>The solid state self–assembly of the tripodal receptors with halide anions was investigated by</div><div>X-ray crystallography. The nature of the structures was dependent on the choice of halide</div><div>anion, as well as the crystallisation solvent. Halogen bond lengths as short as 80% of the sum</div><div>of the van der Waals radii were observed, which is shorter than any halogen bonds involving</div><div>halopyridinium receptors in the Cambridge Structural Database.</div>

Anion Templated Crystal Engineering of Halogen Bonding Tripodal Tris(halopyridinium) Compounds

2020 ◽  
Author(s):  
Emer Foyle ◽  
Nicholas White
Keyword(s):  
Crystal Engineering ◽  
Self Assembly ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Halogen Bonds ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Structural Database ◽  
Van Der Waals Radii

<div>In this work four new tripodal tris(halopyridinium) receptors containing potentially halogen</div><div>bonding groups were prepared. The ability of the receptors to bind anions in competitive</div><div>CD<sub>3</sub>CN/d<sub>6</sub>-DMSO was studied using <sup>1</sup>H NMR titration experiments, which revealed that the</div><div>receptors bind chloride anions more strongly than more basic acetate or other halide ions.</div><div>The solid state self–assembly of the tripodal receptors with halide anions was investigated by</div><div>X-ray crystallography. The nature of the structures was dependent on the choice of halide</div><div>anion, as well as the crystallisation solvent. Halogen bond lengths as short as 80% of the sum</div><div>of the van der Waals radii were observed, which is shorter than any halogen bonds involving</div><div>halopyridinium receptors in the Cambridge Structural Database.</div>

Halogen-bond driven self-assembly of perfluorocarbon monolayers on silicon nitride

2019 ◽  
Vol 7 (42) ◽  
pp. 24445-24453 ◽  
Author(s):  
Antonio Abate ◽  
Raphael Dehmel ◽  
Alessandro Sepe ◽  
Ngoc Linh Nguyen ◽  
Bart Roose ◽  
...  
Keyword(s):  
Silicon Nitride ◽  
Self Assembly ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Self Assembled Monolayers ◽  
Assembled Monolayers ◽  
Self Assembled

We demonstrate that self-assembled monolayers of reproducible thickness can be formed on silicon nitride, driven by halogen bonding using iodo-perfluorinated molecules.

scholarly journals Halogen-Bonding-Driven Self-Assembly of Solvates of Tetrabromoterephthalic Acid

Crystals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 198
Author(s):  
Nucharee Chongboriboon ◽  
Kodchakorn Samakun ◽  
Winya Dungkaew ◽  
Filip Kielar ◽  
Mongkol Sukwattanasinitt ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Phase Transitions ◽  
Self Assembly ◽  
Solid Phase ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Cooperative Effect ◽  
Hydrogen Bonding Interactions ◽  
Solvent Molecules

Halogen bonding is one of the most interesting noncovalent attractions capable of self-assembly and recognition processes in both solution and solid phase. In this contribution, we report on the formation of two solvates of tetrabromoterephthalic acid (H2Br4tp) with acetonitrile (MeCN) and methanol (MeOH) viz. H2Br4tp·2MeCN (1MeCN) and H2Br4tp·2MeOH (2MeOH). The host structures of both 1MeCN and 2MeOH are assembled via the occurrence of simultaneous Br···Br, Br···O, and Br···π halogen bonding interactions, existing between the H2Br4tp molecular tectons. Among them, the cooperative effect of the dominant halogen bond in combination with hydrogen bonding interactions gave rise to different supramolecular assemblies, whereas the strength of the halogen bond depends on the type of hydrogen bond between the molecules of H2Br4tp and the solvents. These materials show a reversible release/resorption of solvent molecules accompanied by evident crystallographic phase transitions.

scholarly journals Crystallographic insights into the structural aspects of thioctic acid based halogen-bond donor for the functionalization of gold nanoparticles

2017 ◽  
Vol 73 (2) ◽  
pp. 240-246 ◽  
Author(s):  
Kavitha Buntara Sanjeeva ◽  
Ilaria Tirotta ◽  
Vijith Kumar ◽  
Francesca Baldelli Bombelli ◽  
Giancarlo Terraneo ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Gold Nanoparticles ◽  
Self Assembly ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Thioctic Acid ◽  
Halogen Bonds ◽  
Donor Ligand ◽  
Structural Aspects

The synthesis and self-assembly capabilities of a new halogen-bond donor ligand, 2,3,5,6-tetrafluoro-4-iodophenyl 5-(1,2-dithiolan-3-yl)pentanoate (1), are reported. The crystal structure of ligand (1) and the formation of a cocrystal with 1,2-di(4-pyridyl)ethylene, (1)·(2), both show halogen bonds involving the 4-iodotetrafluorobenzene moiety. Ligand (1), being a self-complementary unit, forms an infinite halogen-bonded chain driven by the S...I synthon, while the cocrystal (1)·(2) self-assembles into a discrete trimeric entity driven by the N...I synthon. Ligand (1) was also successfully used to functionalize the surface of gold nanoparticles, AuNP-(1). Experiments on the dispersibility profile of AuNP-(1) demonstrated the potential of halogen bonding in facilitating the dispersion of modified NPs with halogen-bond donors in pyridine.

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