Modulating the assembly of N-benzylideneaniline by halogen bonding: crystal, cocrystal and liquid crystals

CrystEngComm ◽  
2017 ◽  
Vol 19 (27) ◽  
pp. 3801-3807 ◽  
Author(s):  
Yufei Wang ◽  
Hongxing Shang ◽  
Bao Li ◽  
Houyu Zhang ◽  
Shimei Jiang
Keyword(s):  
Liquid Crystals ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Π Interactions ◽  
Donor Acceptor

A halogen bond donor–acceptor N-benzylideneaniline self-assembles into an unusual head-to-head chain and a fishbone-like array by C–I⋯π and π⋯π interactions. Furthermore, it forms halogen-bonded cocrystal and liquid crystals with 4,4′-bipyridine or 4-alkoxystilbazole.

scholarly journals The Effect of Pressure on Halogen Bonding in 4-Iodobenzonitrile

Molecules ◽  
2019 ◽  
Vol 24 (10) ◽  
pp. 2018 ◽  
Author(s):  
Nico Giordano ◽  
Sergejs Afanasjevs ◽  
Christine M. Beavers ◽  
Claire L. Hobday ◽  
Konstantin V. Kamenev ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Halogen Bond ◽  
Ambient Pressure ◽  
Halogen Bonding ◽  
Optical Transmittance ◽  
Monoclinic Space Group ◽  
Ambient Conditions ◽  
Π Interactions ◽  
Transparent Crystal ◽  
Triclinic Phase

The crystal structure of 4-iodobenzonitrile, which is monoclinic (space group I2/a) under ambient conditions, contains chains of molecules linked through C≡N···I halogen-bonds. The chains interact through CH···I, CH···N and π-stacking contacts. The crystal structure remains in the same phase up to 5.0 GPa, the b axis compressing by 3.3%, and the a and c axes by 12.3 and 10.9 %. Since the chains are exactly aligned with the crystallographic b axis these data characterise the compressibility of the I···N interaction relative to the inter-chain interactions, and indicate that the halogen bond is the most robust intermolecular interaction in the structure, shortening from 3.168(4) at ambient pressure to 2.840(1) Å at 5.0 GPa. The π∙∙∙π contacts are most sensitive to pressure, and in one case the perpendicular stacking distance shortens from 3.6420(8) to 3.139(4) Å. Packing energy calculations (PIXEL) indicate that the π∙∙∙π interactions have been distorted into a destabilising region of their potentials at 5.0 GPa. The structure undergoes a transition to a triclinic ( P 1 ¯ ) phase at 5.5 GPa. Over the course of the transition, the initially colourless and transparent crystal darkens on account of formation of microscopic cracks. The resistance drops by 10% and the optical transmittance drops by almost two orders of magnitude. The I···N bond increases in length to 2.928(10) Å and become less linear [<C−I∙∙∙N = 166.2(5)°]; the energy stabilises by 2.5 kJ mol−1 and the mixed C-I/I..N stretching frequency observed by Raman spectroscopy increases from 249 to 252 cm−1. The driving force of the transition is shown to be relief of strain built-up in the π∙∙∙π interactions rather than minimisation of the molar volume. The triclinic phase persists up to 8.1 GPa.

scholarly journals Inclusion complexes of Cethyl-2-methylresorcinarene and pyridine N-oxides: breaking the C–I⋯−O–N+ halogen bond by host–guest complexation

CrystEngComm ◽  
2016 ◽  
Vol 18 (5) ◽  
pp. 793-799 ◽  
Author(s):  
Rakesh Puttreddy ◽  
Ngong Kodiah Beyeh ◽  
Kari Rissanen
Keyword(s):  
Inclusion Complexes ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Π Interactions ◽  
Guest Chemistry

Cethyl-2-Methylresorcinarene and aromatic N-oxides manifest host–guest chemistry by C–H⋯π interactions and halogen bonding; the C–I⋯−O–N+ halogen bond with 2-iodopyridine N-oxide is broken by the in-cavity C–I⋯π interactions.

Halogen bonding in uranyl and neptunyl trichloroacetates with alkali metals and improved crystal chemical formulae for coordination compounds

2021 ◽  
Vol 50 (12) ◽  
pp. 4210-4218
Author(s):  
Anton V. Savchenkov ◽  
Andrei S. Uhanov ◽  
Mikhail S. Grigoriev ◽  
Aleksandr M. Fedoseev ◽  
Denis V. Pushkin ◽  
...  
Keyword(s):  
Coordination Compounds ◽  
Alkali Metals ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Crystal Chemical ◽  
Coordination Modes ◽  
Ligand Coordination ◽  
Donor Acceptor

A new donor–acceptor halogen bond synthon is recognized and the notation of ligand coordination modes and crystal chemical formulae is improved.

Photoresponsive ionic liquid crystals assembled via halogen bond: en route towards light-controllable ion transporters

2017 ◽  
Vol 203 ◽  
pp. 407-422 ◽  
Author(s):  
Marco Saccone ◽  
Francisco Fernandez Palacio ◽  
Gabriella Cavallo ◽  
Valentina Dichiarante ◽  
Matti Virkki ◽  
...  
Keyword(s):  
Phase Transition ◽  
Ionic Liquid ◽  
Liquid Crystals ◽  
Uv Light ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Supramolecular Complexes ◽  
Isotropic Phase ◽  
Ionic Liquid Crystals ◽  
Azobenzene Derivatives

We demonstrate that halogen bonding (XB) can offer a novel approach for the construction of photoresponsive ionic liquid crystals. In particular, we assembled two new supramolecular complexes based on 1-ethyl-3-methylimidazolium iodides and azobenzene derivatives containing an iodotetrafluoro-benzene ring as XB donor, where the iodide anion acted as an XB acceptor. DSC and X-ray diffraction analyses revealed that the preferred stoichiometry between the XB donors and acceptors is 2 : 1, and that the iodide anions act as bidentate XB-acceptors, binding two azobenzene derivatives. Due to the high directionality of the XB, calamitic superanions are obtained, while the segregation occurring between the charged and uncharged parts of the molecules gives rise to a layered structure in the crystal lattice. Despite the fact that the starting materials are non-mesomorphic, the halogen-bonded supramolecular complexes exhibited monotropic lamellar liquid-crystalline phases over broad temperature ranges, as confirmed with polarized optical microscopy. Due to the presence of the azobenzene moieties, the LCs were photoresponsive, and a LC-to-isotropic phase transition could be obtained by irradiation with UV light. We envisage that the light-induced phase transition, in combination with the ionic nature of the LC, provides a route towards light-induced control over ion transport and conductance in these supramolecular complexes.

Structural effects of halogen bonding in iodochalcones

2021 ◽  
Vol 77 (3) ◽  
Author(s):  
Victoria Hamilton ◽  
Connah Harris ◽  
Charlie L. Hall ◽  
Jason Potticary ◽  
Matthew E. Cremeens ◽  
...  
Keyword(s):  
Nitro Group ◽  
Crystal Engineering ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Structural Motif ◽  
Halogen Bonds ◽  
Linear Motif ◽  
Hole Making ◽  
Donor Acceptor ◽  
The Impact

The structures of three iodochalcones, functionalized with fluorine or a nitro group, have been investigated to explore the impact of different molecular electrostatic distributions on the halogen bonding within each crystal structure. The strongly withdrawing nitro group presented a switch of the halogen bond from a lateral to a linear motif. Surprisingly, this appears to be influenced by a net positive shift in charge distribution around the lateral edges of the σ-hole, making the lateral I...I bonding motif less preferable. A channel of amphoteric I...I type II halogen bonds is observed for a chalcone molecule, which was not previously reported in chalcones, alongside an example of the common synthon involving extended linear chains of I...O2N donor–acceptor halogen bonds. This work shows that halogenated chalcones may be an interesting target for developing halogen bonding as a significant tool within crystal engineering, a thus far underexplored area for this common structural motif.

scholarly journals Tuning the solid-state emission of liquid crystalline nitro-cyanostilbene by halogen bonding

2021 ◽  
Vol 17 ◽  
pp. 124-131
Author(s):  
Subrata Nath ◽  
Alexander Kappelt ◽  
Matthias Spengler ◽  
Bibhisan Roy ◽  
Jens Voskuhl ◽  
...  
Keyword(s):  
Liquid Crystals ◽  
Solid State ◽  
Bond Strength ◽  
Self Assembly ◽  
Liquid Crystalline ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Systematic Variation ◽  
Mesomorphic Properties

The first example of halogen-bonded fluorescent liquid crystals based on the interaction of iodofluorobenzene derivatives with nitro-cyanostilbenes is reported. The systematic variation of the fluorination degree and pattern indicates the relevance of the halogen bond strength for the induction of liquid crystalline properties. The modular self-assembly approach enables the efficient tuning of the fluorescence behaviour and mesomorphic properties of the assemblies.

scholarly journals Adenine as a Halogen Bond Acceptor: A Combined Experimental and DFT Study

Crystals ◽  
2019 ◽  
Vol 9 (4) ◽  
pp. 224 ◽  
Author(s):  
Yannick Roselló ◽  
Mónica Benito ◽  
Elies Molins ◽  
Miquel Barceló-Oliver ◽  
Antonio Frontera
Keyword(s):  
Density Functional ◽  
Halogen Bond ◽  
Lone Pair ◽  
Halogen Bonding ◽  
Density Functional Theory Calculations ◽  
Functional Theory ◽  
Adenine Ring ◽  
Bonding Interaction ◽  
Donor Ability ◽  
Adenine Derivative

In this work, we report the cocrystallization of N9-ethyladenine with 1,2,4,5-tetrafluoro-3,6-diiodobenzene (TFDIB), a classical XB donor. As far as our knowledge extends, this is the first cocrystal reported to date where an adenine derivative acts as a halogen bond acceptor. In the solid state, each adenine ring forms two centrosymmetric H-bonded dimers: one using N1···HA6–N6 and the other N7···HB6–N6. Therefore, only N3 is available as a halogen bond acceptor that, indeed, establishes an N···I halogen bonding interaction with TFDIB. The H-bonded dimers and halogen bonds have been investigated via DFT (Density Functional Theory) calculations and the Bader’s Quantum Theory of Atoms In Molecules (QTAIM) method at the B3LYP/6-311+G* level of theory. The influence of H-bonding interactions on the lone pair donor ability of N3 has also been analyzed using the molecular electrostatic potential (MEP) surface calculations.

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.

Cooperative halogen bonding and polarized π-stacking in the formation of coloured charge-transfer co-crystals

2018 ◽  
Vol 42 (13) ◽  
pp. 10615-10622 ◽  
Author(s):  
Chideraa I. Nwachukwu ◽  
Zachary R. Kehoe ◽  
Nathan P. Bowling ◽  
Erin D. Speetzen ◽  
Eric Bosch
Keyword(s):  
Charge Transfer ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Π Stacking

Matched electron rich halogen bond acceptors and donor have been synthesized and the halogen bonded charge transfer cocrystals characterized.

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....

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