Supramolecular assembly in metal complexes: Two structural cases

2013 ◽  
Vol 85 (2) ◽  
pp. 397-404 ◽  
Author(s):  
Mohamed Ghazzali
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Theoretical Calculations ◽  
Supramolecular Assembly ◽  
Halogen Bonding ◽  
One Pot ◽  
Iron Coordination ◽  
Structural Database ◽  
Molecular Components ◽  
Theoretical Analyses

With the current advances in our understanding of molecular components in the solid-state world, the relation between energy and geometry remains controversial. In this study, we deliver a concise account for supramolecular chemistry, and in order to illustrate some of its concepts we describe some structural and theoretical analyses for two unique cases of our work. We elaborate on a supramolecular model of controlled “one-pot” host–guest metal-mediated self-assembly reaction inside iron coordination polymer grid architecture, and we review halogen bonding by specifically observing M–Cl···Cl–M intermolecular interactions using Cambridge Structural Database (CSD) hit analyses with theoretical calculations.

Harnessing uranyl oxo atoms via halogen bonding interactions in molecular uranyl materials featuring 2,5-diiodobenzoic acid and N-donor capping ligands

2017 ◽  
Vol 4 (1) ◽  
pp. 65-78 ◽  
Author(s):  
Korey P. Carter ◽  
Mark Kalaj ◽  
Christopher L. Cahill
Keyword(s):  
Solid State ◽  
Supramolecular Assembly ◽  
Halogen Bonding ◽  
Capping Ligands

The supramolecular assembly of molecular uranyl species via halogen-oxo interactions and spectroscopic manifestations thereof are probed in the solid state.

scholarly journals {N 1-[2-(Butylselanyl)benzyl]-N 2,N 2-dimethylethane-1,2-diamine}dichloridomercury(II)

2018 ◽  
Vol 74 (8) ◽  
pp. 1151-1154
Author(s):  
Pushpendra Singh ◽  
Harkesh B. Singh ◽  
Ray J. Butcher
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Self Assembly ◽  
Title Compound ◽  
Supramolecular Assembly ◽  
Molecular Geometry ◽  
The Self ◽  
Intermolecular Hydrogen Bonding ◽  
Hydrogen Bonding Interactions ◽  
Donor Acceptor

In the title compound, [HgCl2(C16H28N2Se)], the primary geometry around the Se and Hg atoms is distorted trigonal–pyramidal and distorted square-pyramidal, respectively. The distortion of the molecular geometry in the complex is caused by the steric demands of the ligands attached to the Se atom. The Hg atom is coordinated through two chloride anions, an N atom and an Se atom, making up an unusual HgNSeCl2 coordination sphere with an additional long Hg...N interaction. Intermolecular C—H...Cl interactions are the only identified intermolecular hydrogen-bonding interactions that seem to be responsible for the self assembly. These relatively weak C—H...Cl hydrogen bonds possess the required linearity and donor–acceptor distances. They act as molecular associative forces that result in a supramolecular assembly along the b-axis direction in the solid state of the title compound.

scholarly journals Revealing molecular self-assembly and geometry of non-covalent halogen bonding by solid-state NMR spectroscopy

2008 ◽  
pp. 5981 ◽  
Author(s):  
Markus Weingarth ◽  
Noureddine Raouafi ◽  
Benjamin Jouvelet ◽  
Luminita Duma ◽  
Geoffrey Bodenhausen ◽  
...  
Keyword(s):  
Solid State ◽  
Nmr Spectroscopy ◽  
Self Assembly ◽  
Solid State Nmr ◽  
Halogen Bonding ◽  
Solid State Nmr Spectroscopy

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 Hierarchical supramolecular assembly of a single peptoid polymer into a planar nanobrush with two distinct molecular packing motifs

2020 ◽  
Vol 117 (50) ◽  
pp. 31639-31647
Author(s):  
Jing Sun ◽  
Zhiwei Wang ◽  
Chenhui Zhu ◽  
Meiyao Wang ◽  
Zhekun Shi ◽  
...  
Keyword(s):  
Diblock Copolymer ◽  
Self Assembly ◽  
Elevated Temperatures ◽  
Protein Crystallization ◽  
Supramolecular Assembly ◽  
Molecular Packing ◽  
One Pot ◽  
Precise Control ◽  
Assembly Mechanism ◽  
Copolymer Poly

Hierarchical nanomaterials have received increasing interest for many applications. Here, we report a facile programmable strategy based on an embedded segmental crystallinity design to prepare unprecedented supramolecular planar nanobrush-like structures composed of two distinct molecular packing motifs, by the self-assembly of one particular diblock copolymer poly(ethylene glycol)-block-poly(N-octylglycine) in a one-pot preparation. We demonstrate that the superstructures result from the temperature-controlled hierarchical self-assembly of preformed spherical micelles by optimizing the crystallization−solvophobicity balance. Particularly remarkable is that these micelles first assemble into linear arrays at elevated temperatures, which, upon cooling, subsequently template further lateral, crystallization-driven assembly in a living manner. Addition of the diblock copolymer chains to the growing nanostructure occurs via a loosely organized micellar intermediate state, which undergoes an unfolding transition to the final crystalline state in the nanobrush. This assembly mechanism is distinct from previous crystallization-driven approaches which occur via unimer addition, and is more akin to protein crystallization. Interestingly, nanobrush formation is conserved over a variety of preparation pathways. The precise control ability over the superstructure, combined with the excellent biocompatibility of polypeptoids, offers great potential for nanomaterials inaccessible previously for a broad range of advanced applications.

Photoresponsive Organogel Based on Supramolecular Assembly of Tris(phenylisoxazolyl)benzene

2010 ◽  
Vol 63 (4) ◽  
pp. 640 ◽  
Author(s):  
Takeharu Haino ◽  
Hiroshi Saito
Keyword(s):  
Structural Change ◽  
Solid State ◽  
Trans Isomer ◽  
Self Assembly ◽  
Uv Light ◽  
Supramolecular Assembly ◽  
The Self ◽  
Solvent Molecules ◽  
Supramolecular Networks ◽  
Cis Isomer

Azobenzene-substituted tris(phenylisoxazolyl)benzene 1 was developed as a photoresponsive gelator. A detailed study of the self-assembly of the trans- and cis-isomers in solution revealed that the planar trans-isomer assembled to form molecular stacks along its C 3 axis, whereas the cis-isomer did not owing to steric requirements. Based on diffusion ordered spectroscopy experiments, the size of the aggregates formed from the trans-isomer were roughly four times as large as those of the cis-isomer. The photoinduced gel-to-sol transition was achieved by irradiation with UV light at 360 nm. Solid-state morphologies of the trans- and cis-isomers were quite contrastive; the trans-isomer created fibrous supramolecular networks with a lot of voids in which solvent molecules could be immobilized, whereas the cis-isomer never created such fibrous morphologies. The trans–cis structural change of the azobenzene moieties obviously regulates the gelation ability of 1.

Halogen bonding directed supramolecular assembly in bromo-substituted trezimides and tennimides

CrystEngComm ◽  
2014 ◽  
Vol 16 (10) ◽  
pp. 1893-1903 ◽  
Author(s):  
Pavle Mocilac ◽  
John F. Gallagher
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Crystal Structures ◽  
Supramolecular Assembly ◽  
Halogen Bonding ◽  
Strong Hydrogen Bond ◽  
Aggregation Process ◽  
Halogen Bonds ◽  
State Aggregation ◽  
Hydrogen Bond Donors

The imide-based trezimide and tennimide macrocycle crystal structures typically aggregate as 1-D chains through C–Br⋯OC/N/π(arene) halogen bonds (withNc≤ 0.90) that dominate the solid-state aggregation process in the absence of classical strong hydrogen bond donors.

scholarly journals Halogenated Diazabutadiene Dyes: Synthesis, Structures, Supramolecular Features, and Theoretical Studies

Molecules ◽  
2020 ◽  
Vol 25 (21) ◽  
pp. 5013
Author(s):  
Valentine G. Nenajdenko ◽  
Namiq G. Shikhaliyev ◽  
Abel M. Maharramov ◽  
Khanim N. Bagirova ◽  
Gulnar T. Suleymanova ◽  
...  
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Topological Analysis ◽  
Halogen Bonding ◽  
Fine Tuning ◽  
Theoretical Studies ◽  
X Ray Diffraction ◽  
1H And 13C Nmr ◽  
X Ray ◽  
Nmr Techniques

Novel halogenated aromatic dichlorodiazadienes were prepared via copper-mediated oxidative coupling between the corresponding hydrazones and CCl4. These rare azo-dyes were characterized using 1H and 13C NMR techniques and X-ray diffraction analysis for five halogenated dichlorodiazadienes. Multiple non-covalent halogen···halogen interactions were detected in the solid state and studied by DFT calculations and topological analysis of the electron density distribution within the framework of Bader’s theory (QTAIM method). Theoretical studies demonstrated that non-covalent halogen···halogen interactions play crucial role in self-assembly of highly polarizable dichlorodiazadienes. Thus, halogen bonding can dictate a packing preference in the solid state for this class of dichloro-substituted heterodienes, which could be a convenient tool for a fine tuning of the properties of this novel class of dyes.

scholarly journals Solid-State Fluorescence Enhancement of Bromine-Substituted Trans-Enaminone Derivatives

2020 ◽  
Vol 02 (01) ◽  
pp. 033-040 ◽  
Author(s):  
Hua Li ◽  
Haiyang Shu ◽  
Xin Wang ◽  
Xiaofu Wu ◽  
Hongkun Tian ◽  
...  
Keyword(s):  
Solid State ◽  
Quantum Yield ◽  
Decay Rate ◽  
Fluorescence Quantum Yield ◽  
Radiative Decay ◽  
Theoretical Calculations ◽  
Halogen Bonding ◽  
Radiative Decay Rate ◽  
Solid State Fluorescence ◽  
High Fluorescence

Halogen bonding, as a kind of intermolecular interaction, has rarely been used to tune solid-state emission properties of luminescent materials, especially fluorescent materials. Herein, three trans-enaminone (TE) derivatives (nonbrominated TE, monobrominated BrTE, and tribrominated Br3TE) with aggregation-induced emission property have been designed and synthesized. Two types of BrTE crystals (BrTE-B and BrTE-G) with different fluorescence properties were obtained. It was observed that their solid-state fluorescence has been enhanced by the formation of halogen bonding. In particular, the crystal BrTE-G containing Br…π interactions exhibits a fluorescence quantum yield (9.6%) nearly sevenfold higher than BrTE-B, the crystal without halogen bonding (1.4%), and fivefold higher than the nonbrominated TE derivative (2.1%). By careful inspection of the single-crystal data and theoretical calculations, the high fluorescence quantum yield of BrTE-G appears to be due to halogen-bonding interactions as well as multiple stronger intermolecular interactions which may restrain molecular motions, leading to the reduced nonradiative decay rate and the enhanced radiative decay rate. Additionally, increasing the number of bromine substituents may further promote the radiative decay rate, explaining therefore the higher fluorescence quantum yield (12.5%) of Br3TE.

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