A family of powerful halogen-bond donors: A structural and theoretical analysis of triply activated 3-iodo-1-phenylprop-2-yn-1-ones

CrystEngComm ◽  
2022 ◽  
Author(s):  
Vinu V Panikkattu ◽  
Abhijeet Shekhar Sinha ◽  
Christer Aakeröy
Keyword(s):  
Theoretical Analysis ◽  
Self Assembly ◽  
Halogen Bond ◽  
Functional Materials ◽  
Halogen Bonds ◽  
New Class

Strong halogen bonds can provide a foundation for reliable supramolecular strategies for effective self-assembly and design of functional materials. A new class of halogen-bond donors have been developed using structural...

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>

scholarly journals C—I...N and C—I...π halogen bonding in the structures of 1-benzyliodoimidazole derivatives

2017 ◽  
Vol 73 (1) ◽  
pp. 2-8 ◽  
Author(s):  
Chideraa I. Nwachukwu ◽  
Nathan P. Bowling ◽  
Eric Bosch
Keyword(s):  
Intermolecular Interaction ◽  
Intermolecular Interactions ◽  
Halogen Bond ◽  
Three Dimensional ◽  
Functional Materials ◽  
Halogen Bonding ◽  
Dimensional Structure ◽  
Halogen Bonds ◽  
One Dimensional ◽  
X Ray

Halogen bonding is a well-established and intensively studied intermolecular interaction that has also been used in the preparation of functional materials. While polyfluoroiodo- and polyfluorobromobenzenes have been widely used as aromatic halogen-bond donors, there have been very few studies of iodoimidazoles with regard to halogen bonding. We describe here the X-ray structures of three iodoimidazole derivatives, namely 1-benzyl-2-iodo-1H-imidazole, C10H9IN2, (1), 1-benzyl-4-iodo-1H-imidazole, C10H9IN2, (2), and 1-benzyl-2-iodo-1H-benzimidazole, C14H11IN2, (3), and the halogen bonds that dominate the intermolecular interactions in each of these three structures. The three-dimensional structure of (1) is dominated by a strong C—I...N halogen bond, with an N...I distance of 2.8765 (2) Å, that connects the molecules into one-dimensional zigzag ribbons of molecules. In contrast, the three-dimensional structures of (2) and (3) both feature C—I...π halogen-bonded dimers.

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.

Halogen-bond driven self-assembly of triangular macrocycles

2018 ◽  
Vol 42 (13) ◽  
pp. 10467-10471 ◽  
Author(s):  
Patrick M. J. Szell ◽  
Antti Siiskonen ◽  
Luca Catalano ◽  
Gabriella Cavallo ◽  
Giancarlo Terraneo ◽  
...  
Keyword(s):  
Self Assembly ◽  
Halogen Bond ◽  
The Self ◽  
Halogen Bonds ◽  
Methyl Imidazole

Halogen bonds drive the self-assembly of 2-iodoethynylpyridine and 2- iodoethynyl-1-methyl-imidazole into discrete supramolecular triangles.

Crystalline assemblies of porphyrins with mixed bromophenyl and pyridyl meso-substituents and manifestation of supramolecular chirality induced by inter-porphyrin Br⋯N halogen bonds

2011 ◽  
Vol 15 (11n12) ◽  
pp. 1250-1257 ◽  
Author(s):  
Hatem M. Titi ◽  
Anirban Karmakar ◽  
Israel Goldberg
Keyword(s):  
Self Assembly ◽  
Halogen Bond ◽  
Supramolecular Assembly ◽  
Halogen Bonding ◽  
Building Blocks ◽  
Zinc Ion ◽  
Halogen Bonds ◽  
X Ray Diffraction ◽  
Supramolecular Chirality ◽  
Porphyrin Core

Four new crystalline solids based on the zinc-5,15-bis(4′-bromophenyl)-10,20- bis(4′-pyridyl)porphyrin ( Zn –DBDPyP) and zinc/copper-5,10,15-tris(4′-bromophenyl)-20-(4′-pyridyl)-porphyrin ( Zn/Cu –TBMPyP) platforms as building blocks, have been prepared and structurally analyzed by X-ray diffraction in order to examine whether the Br⋯N halogen bond can be effective in directing the supramolecular assembly of this functionalized porphyrins, in a similar way observed earlier for their iodophenyl-substituted analogs. The zinc ion in the porphyrin core was protected by an external ligand (pyridyl or methanol) to prevent its possible coordination to the pyridyl-porphyrin substituents. Neither the bis-pyridyl Zn (py)–DBDPyP scaffold nor the Zn(MeOH)/Cu –TBMPyP exhibited inter-porphyrin halogen bonding in their corresponding crystals. Only the layered self-assembly of the Zn (py)–TBMPyP building block was found to be uniquely directed by Br⋯N halogen bonds, as well as by Br⋯Br and Br⋯π interactions. This observation supports our notion that asymmetric functionalization of the tetraarylporphyrin scaffold, combined with directional interporphyrin interactions (as halogen bonding), represent a promising approach to supramolecular chirality.

scholarly journals Surface-controlled reversal of the selectivity of halogen bonds

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Jalmar Tschakert ◽  
Qigang Zhong ◽  
Daniel Martin-Jimenez ◽  
Jaime Carracedo-Cosme ◽  
Carlos Romero-Muñiz ◽  
...  
Keyword(s):  
Gas Phase ◽  
Self Assembly ◽  
Organic Molecules ◽  
Halogen Bond ◽  
Control Parameters ◽  
Halogen Bonds ◽  
Molecular Assemblies ◽  
Molecular Charge ◽  
Different Types ◽  
Bond Strengths

Abstract Intermolecular halogen bonds are ideally suited for designing new molecular assemblies because of their strong directionality and the possibility of tuning the interactions by using different types of halogens or molecular moieties. Due to these unique properties of the halogen bonds, numerous areas of application have recently been identified and are still emerging. Here, we present an approach for controlling the 2D self-assembly process of organic molecules by adsorption to reactive vs. inert metal surfaces. Therewith, the order of halogen bond strengths that is known from gas phase or liquids can be reversed. Our approach relies on adjusting the molecular charge distribution, i.e., the σ-hole, by molecule-substrate interactions. The polarizability of the halogen and the reactiveness of the metal substrate are serving as control parameters. Our results establish the surface as a control knob for tuning molecular assemblies by reversing the selectivity of bonding sites, which is interesting for future applications.

scholarly journals Nanoscale Crystalline Sheets and Vesicles Assembled from Nonplanar Cyclic π-Conjugated Molecules

Research ◽  
2019 ◽  
Vol 2019 ◽  
pp. 1-11 ◽  
Author(s):  
Huang Tang ◽  
Zhewei Gu ◽  
Haifeng Ding ◽  
Zhibo Li ◽  
Shiyan Xiao ◽  
...  
Keyword(s):  
Self Assembly ◽  
Carbon Nanomaterials ◽  
Materials Science ◽  
Functional Materials ◽  
Building Blocks ◽  
Molecular Scaffolds ◽  
Conjugated Molecules ◽  
New Class ◽  
Supramolecular Architectures ◽  
Cyclic Molecules

A fundamental challenge in chemistry and materials science is to create new carbon nanomaterials by assembling structurally unique carbon building blocks, such as nonplanar π-conjugated cyclic molecules. However, self-assembly of such cyclic π-molecules to form organized nanostructures has been rarely explored despite intensive studies on their chemical synthesis. Here we synthesized a family of new cycloparaphenylenes and found that these fully hydrophobic and nonplanar cyclic π-molecules could self-assemble into structurally distinct two-dimensional crystalline multilayer nanosheets. Moreover, these crystalline multilayer nanosheets could overcome inherent rigidity to curve into closed crystalline vesicles in solution. These supramolecular assemblies show that the cyclic molecular scaffolds are homogeneously arranged on the surface of nanosheets and vesicles with their molecular isotropic x-y plane standing obliquely on the surface. These supramolecular architectures that combined exact crystalline order, orientation-specific arrangement of π-conjugated cycles, controllable morphology, uniform molecular pore, superior florescence quench ability, and photoluminescence are expected to give rise to a new class of functional materials displaying unique photonic, electronic, and biological functions.

A Bottom-Up Approach to Solution-Processed, Atomically Precise Graphitic Cylinders on Surfaces

2018 ◽  
Author(s):  
Erik Leonhardt ◽  
Jeff M. Van Raden ◽  
David Miller ◽  
Lev N. Zakharov ◽  
Benjamin Aleman ◽  
...  
Keyword(s):  
Self Assembly ◽  
Carbon Nanostructures ◽  
Carbon Nanomaterials ◽  
Circle Packing ◽  
Pyrolytic Graphite ◽  
Building Blocks ◽  
Bottom Up ◽  
Casting Technique ◽  
New Class ◽  
Solution Casting Technique

Extended carbon nanostructures, such as carbon nanotubes (CNTs), exhibit remarkable properties but are difficult to synthesize uniformly. Herein, we present a new class of carbon nanomaterials constructed via the bottom-up self-assembly of cylindrical, atomically-precise small molecules. Guided by supramolecular design principles and circle packing theory, we have designed and synthesized a fluorinated nanohoop that, in the solid-state, self-assembles into nanotube-like arrays with channel diameters of precisely 1.63 nm. A mild solution-casting technique is then used to construct vertical “forests” of these arrays on a highly-ordered pyrolytic graphite (HOPG) surface through epitaxial growth. Furthermore, we show that a basic property of nanohoops, fluorescence, is readily transferred to the bulk phase, implying that the properties of these materials can be directly altered via precise functionalization of their nanohoop building blocks. The strategy presented is expected to have broader applications in the development of new graphitic nanomaterials with π-rich cavities reminiscent of CNTs.

Unique Functional Materials Derived from β-Amino Acid Oligomers

2017 ◽  
Vol 70 (2) ◽  
pp. 126 ◽  
Author(s):  
Mark P. Del Borgo ◽  
Ketav Kulkarni ◽  
Marie-Isabel Aguilar
Keyword(s):  
Amino Acid ◽  
Drug Design ◽  
Self Assembly ◽  
Functional Materials ◽  
Bioactive Molecules ◽  
Peptide Drug ◽  
New Materials ◽  
Amino Acid Oligomers

The unique structures formed by β-amino acid oligomers, or β-peptide foldamers, have been studied for almost two decades, which has led to the discovery of several distinctive structures and bioactive molecules. Recently, this area of research has expanded from conventional peptide drug design to the formation of assemblies and nanomaterials by peptide self-assembly. The unique structures formed by β-peptides give rise to a set of new materials with altered properties that differ from conventional peptide-based materials; such new materials may be useful in several bio- and nanomaterial applications.

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