scholarly journals Halogen bonding stabilizes acis-azobenzene derivative in the solid state: a crystallographic study

2017 ◽  
Vol 73 (2) ◽  
pp. 227-233 ◽  
Author(s):  
Marco Saccone ◽  
Antti Siiskonen ◽  
Franisco Fernandez-Palacio ◽  
Arri Priimagi ◽  
Giancarlo Terraneo ◽  
...  
Keyword(s):  
Solid State ◽  
Density Functional ◽  
Rational Design ◽  
Halogen Bond ◽  
Phase Segregation ◽  
Halogen Bonding ◽  
Density Functional Theory Calculations ◽  
Aliphatic Chain ◽  
Molecular Arrangement

Crystals oftrans- andcis-isomers of a fluorinated azobenzene derivative have been prepared and characterized by single-crystal X-ray diffraction. The presence of F atoms on the aromatic core of the azobenzene increases the lifetime of the metastablecis-isomer, allowing single crystals of thecis-azobenzene to be grown. Structural analysis on thecis-azobenzene, complemented with density functional theory calculations, highlights the active role of the halogen-bond contact (N...I synthon) in promoting the stabilization of thecis-isomer. The presence of a long aliphatic chain on the azobenzene unit induces a phase segregation that stabilizes the molecular arrangement for both thetrans- andcis-isomers. Due to the rarity ofcis-azobenzene crystal structures in the literature, our paper makes a step towards understanding the role of non-covalent interactions in driving the packing of metastable azobenzene isomers. This is expected to be important in the future rational design of solid-state, photoresponsive materials based on halogen bonding.

Competition between hydrogen and halogen bonding in the structures of 5,10-dihydroxy-5,10-dihydroboranthrenes

2014 ◽  
Vol 70 (1) ◽  
pp. 157-171 ◽  
Author(s):  
Krzysztof Durka ◽  
Sergiusz Luliński ◽  
Katarzyna N. Jarzembska ◽  
Jaromir Smętek ◽  
Janusz Serwatowski ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Density Functional ◽  
Crystal Packing ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Structural Diversity ◽  
Interesting Case ◽  
Molecular Arrangement ◽  
Supramolecular Arrangements

X-ray crystallographic and computational studies are reported for a series of boranthrenes, substituted with halogen atoms. The role of competitive hydrogen (O—H...O, O—H...F, C—H...O) and halogen (Cl...Cl, O...Br, F...F) bonding interactions on the molecular arrangement in the crystal structures is discussed. The structural analysis and calculations reveal that the O—H...O hydrogen bond in the unsubstituted derivative 5,10-dihydroxy-5,10-dihydroboranthrene, C12H10B2O2, is of moderate strength (ca−20 kJ mol−1), but weaker than that in the related thiophene derivative 4,8-dihydro-4,8-dihydroxy-p-diborino[2,3-b:5,6-b]dithiophene, C8H6B2O2S2(ca−40 kJ mol−1). This is due to shielding of the OH group by the H atoms in the β-position of the boranthrene unit. Structural diversity derived from the flexibility of the O—H...O hydrogen bond facilitates the occurrence of other competitive interactions. For instance, in the 1,6-difluoro derivative, C12H8B2F2O2, the crystal packing results from O—H...F and F...F interactions. In turn, the 1,6-dibromo derivative, C12H8B2Br2O2, is dominated by Br...O halogen-bond interactions. In the most interesting case, the 1,6-dichloro derivative, C12H8B2Cl2O2, molecular disorder leads to the formation of two different supramolecular arrangements co-existing in the crystal lattice, one based on the Cl...Cl and C—H...O bonds, and the other stabilized by O—H...O hydrogen bonds. Calculations performed with density-functional theory (DFT;CRYSTAL09) andPIXELmethodologies show that both lattices are characterized by similar energy values (ca−100 kJ mol−1). A mixed arrangement with random or short-range-ordered molecular orientations can also be expected.

A comparative experimental and theoretical investigation of hydrogen-bond, halogen-bond and π–π interactions in the solid-state supramolecular assembly of 2- and 4-formylphenyl arylsulfonates

2018 ◽  
Vol 74 (7) ◽  
pp. 816-829 ◽  
Author(s):  
Hina Andleeb ◽  
Imtiaz Khan ◽  
Antonio Bauzá ◽  
Muhammad Nawaz Tahir ◽  
Jim Simpson ◽  
...  
Keyword(s):  
Solid State ◽  
Density Functional ◽  
Halogen Bond ◽  
Noncovalent Interactions ◽  
Supramolecular Assembly ◽  
Halogen Bonding ◽  
Type I ◽  
Supramolecular Architectures ◽  
Solid State Structures

To explore the operational role of noncovalent interactions in supramolecular architectures with designed topologies, a series of solid-state structures of 2- and 4-formylphenyl 4-substituted benzenesulfonates was investigated. The compounds are 2-formylphenyl 4-methylbenzenesulfonate, C14H12O4S, 3a, 2-formylphenyl 4-chlorobenzenesulfonate, C13H9ClO4S, 3b, 2-formylphenyl 4-bromobenzenesulfonate, C13H9BrO4S, 3c, 4-formylphenyl 4-methylbenzenesulfonate, C14H12O4S, 4a, 4-formylphenyl 4-chlorobenzenesulfonate, 4b, C13H9ClO4S, and 4-formylphenyl 4-bromobenzenesulfonate, C13H9BrO4S, 4c. The title compounds were synthesized under basic conditions from salicylaldehyde/4-hydroxybenzaldehydes and various aryl sulfonyl chlorides. Remarkably, halogen-bonding interactions are found to be important to rationalize the solid-state crystal structures. In particular, the formation of O...X (X = Cl and Br) and type I X...X halogen-bonding interactions have been analyzed by means of density functional theory (DFT) calculations and characterized using Bader's theory of `atoms in molecules' and molecular electrostatic potential (MEP) surfaces, confirming the relevance and stabilizing nature of these interactions. They have been compared to antiparallel π-stacking interactions that are formed between the arylsulfonates.

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.

scholarly journals Halogen bonding, chalcogen bonding, pnictogen bonding, tetrel bonding: origins, current status and discussion

2017 ◽  
Vol 203 ◽  
pp. 485-507 ◽  
Author(s):  
Lee Brammer
Keyword(s):  
Solid State ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Main Group ◽  
Solution Phase ◽  
Current Status ◽  
Solid State Chemistry ◽  
Main Group Elements ◽  
Past Work

The role of the closing lecture in a Faraday Discussion is to summarise the contributions made to the Discussion over the course of the meeting and in so doing capture the main themes that have arisen. This article is based upon my Closing Remarks Lecture at the 203rdFaraday Discussion meeting on Halogen Bonding in Supramolecular and Solid State Chemistry, held in Ottawa, Canada, on 10–12thJuly, 2017. The Discussion included papers on fundamentals and applications of halogen bonding in the solid state and solution phase. Analogous interactions involving main group elements outside group 17 were also examined. In the closing lecture and in this article these contributions have been grouped into the four themes: (a) fundamentals, (b) beyond the halogen bond, (c) characterisation, and (d) applications. The lecture and paper also include a short reflection on past work that has a bearing on the Discussion.

scholarly journals A Flexible Electron-blocking Interfacial Shield for Dendrite-free Solid Lithium Metal Batteries

2020 ◽  
Author(s):  
Hanyu Huo ◽  
Jian Gao ◽  
Ning Zhao ◽  
Dongxing Zhang ◽  
Nathaniel Holmes ◽  
...  
Keyword(s):  
Solid State ◽  
Density Functional ◽  
Rational Design ◽  
Electron Tunneling ◽  
Electronic Conductivity ◽  
Lithium Ion ◽  
Density Functional Theory Calculations ◽  
High Electron ◽  
High Electronic Conductivity ◽  
Battery Technology

Abstract Solid-state batteries (SSBs) are considered to be the next-generation lithium-ion battery technology due to their enhanced energy density and safety. However, the high electronic conductivity of solid-state electrolytes (SSEs) leads to Li dendrite nucleation and proliferation. Uneven electric-field distribution resulting from poor interfacial contact can further promote dendritic deposition and lead to rapid short circuiting of SSBs. Herein, a flexible electron-blocking interfacial shield (EBS) is proposed to protect garnet electrolytes from the electronic degradation. The EBS formed by an in-situ substitution reaction can not only increase lithiophilicity but also stabilize the Li volume change, maintaining the integrity of the interface during repeated cycling. Density functional theory calculations show a high electron-tunneling energy barrier from Li metal to the EBS, indicating an excellent capacity for electron-blocking. EBS protected cells exhibit an improved critical current density of 1.2 mA cm-2 and stable cycling for over 400 h at 1 mA cm-2 (1 mAh cm-2) at room temperature. These results demonstrate an effective strategy for the suppression of Li dendrites and present fresh insight into the rational design of the SSE and Li metal interface.

scholarly journals A flexible electron-blocking interfacial shield for dendrite-free solid lithium metal batteries

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Hanyu Huo ◽  
Jian Gao ◽  
Ning Zhao ◽  
Dongxing Zhang ◽  
Nathaniel Graham Holmes ◽  
...  
Keyword(s):  
Solid State ◽  
Density Functional ◽  
Rational Design ◽  
Electron Tunneling ◽  
Electronic Conductivity ◽  
Lithium Ion ◽  
Density Functional Theory Calculations ◽  
High Electron ◽  
High Electronic Conductivity ◽  
Battery Technology

AbstractSolid-state batteries (SSBs) are considered to be the next-generation lithium-ion battery technology due to their enhanced energy density and safety. However, the high electronic conductivity of solid-state electrolytes (SSEs) leads to Li dendrite nucleation and proliferation. Uneven electric-field distribution resulting from poor interfacial contact can further promote dendritic deposition and lead to rapid short circuiting of SSBs. Herein, we propose a flexible electron-blocking interfacial shield (EBS) to protect garnet electrolytes from the electronic degradation. The EBS formed by an in-situ substitution reaction can not only increase lithiophilicity but also stabilize the Li volume change, maintaining the integrity of the interface during repeated cycling. Density functional theory calculations show a high electron-tunneling energy barrier from Li metal to the EBS, indicating an excellent capacity for electron-blocking. EBS protected cells exhibit an improved critical current density of 1.2 mA cm−2 and stable cycling for over 400 h at 1 mA cm−2 (1 mAh cm−2) at room temperature. These results demonstrate an effective strategy for the suppression of Li dendrites and present fresh insight into the rational design of the SSE and Li metal interface.

13C and 19F solid-state NMR and X-ray crystallographic study of halogen-bonded frameworks featuring nitrogen-containing heterocycles

2017 ◽  
Vol 73 (3) ◽  
pp. 157-167 ◽  
Author(s):  
Patrick M. J. Szell ◽  
Shaina A. Gabriel ◽  
Russell D. D. Gill ◽  
Shirley Y. H. Wan ◽  
Bulat Gabidullin ◽  
...  
Keyword(s):  
Solid State ◽  
Density Functional ◽  
Halogen Bond ◽  
Chemical Shifts ◽  
Halogen Bonding ◽  
Structural Features ◽  
Magic Angle Spinning ◽  
Magic Angle ◽  
X Ray ◽  
Donor And Acceptor

Halogen bonding is a noncovalent interaction between the electrophilic region of a halogen (σ-hole) and an electron donor. We report a crystallographic and structural analysis of halogen-bonded compounds by applying a combined X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (SSNMR) approach. Single-crystal XRD was first used to characterize the halogen-bonded cocrystals formed between two fluorinated halogen-bond donors (1,4-diiodotetrafluorobenzene and 1,3,5-trifluoro-2,4,6-triiodobenzene) and several nitrogen-containing heterocycles (acridine, 1,10-phenanthroline, 2,3,5,6-tetramethylpyrazine, and hexamethylenetetramine). New structures are reported for the following three cocrystals, all in the P21/c space group: acridine–1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C13H9N, 1,10-phenanthroline–1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C12H8N2, and 2,3,5,6-tetramethylpyrazine–1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C8H12N2. 13C and 19F solid-state magic-angle spinning (MAS) NMR is shown to be a convenient method to characterize the structural features of the halogen-bond donor and acceptor, with chemical shifts attributable to cocrystal formation observed in the spectra of both nuclides. Cross polarization (CP) from 19F to 13C results in improved spectral sensitivity in characterizing the perfluorinated halogen-bond donor when compared to conventional 1H CP. Gauge-including projector-augmented wave density functional theory (GIPAW DFT) calculations of magnetic shielding constants, along with optimization of the XRD structures, provide a final set of structures in best agreement with the experimental 13C and 19F chemical shifts. Data for carbons bonded to iodine remain outliers due to well-known relativistic effects.

scholarly journals Polymorphs of Rb3ScF6: X-ray and Neutron Diffraction, Solid-State NMR, and Density Functional Theory Calculations Study

2021 ◽  
Vol 60 (8) ◽  
pp. 6016-6026
Author(s):  
Aydar Rakhmatullin ◽  
Maxim S. Molokeev ◽  
Graham King ◽  
Ilya B. Polovov ◽  
Konstantin V. Maksimtsev ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Solid State ◽  
Neutron Diffraction ◽  
Solid State Nmr ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Functional Theory ◽  
X Ray

scholarly journals Role of Chemistry and Crystal Structure on the Electronic Defect States in Cs-Based Halide Perovskites

Materials ◽  
2021 ◽  
Vol 14 (4) ◽  
pp. 1032
Author(s):  
Anirban Naskar ◽  
Rabi Khanal ◽  
Samrat Choudhury
Keyword(s):  
Crystal Structure ◽  
Density Functional ◽  
Covalent Bond ◽  
Density Functional Theory Calculations ◽  
Antisite Defect ◽  
Defect States ◽  
Functional Theory ◽  
Electronic Defect ◽  
Constituent Elements

The electronic structure of a series perovskites ABX3 (A = Cs; B = Ca, Sr, and Ba; X = F, Cl, Br, and I) in the presence and absence of antisite defect XB were systematically investigated based on density-functional-theory calculations. Both cubic and orthorhombic perovskites were considered. It was observed that for certain perovskite compositions and crystal structure, presence of antisite point defect leads to the formation of electronic defect state(s) within the band gap. We showed that both the type of electronic defect states and their individual energy level location within the bandgap can be predicted based on easily available intrinsic properties of the constituent elements, such as the bond-dissociation energy of the B–X and X–X bond, the X–X covalent bond length, and the atomic size of halide (X) as well as structural characteristic such as B–X–B bond angle. Overall, this work provides a science-based generic principle to design the electronic states within the band structure in Cs-based perovskites in presence of point defects such as antisite defect.

scholarly journals CO2 activation through silylimido and silylamido zirconium hydrides supported on N-donor chelating SBA15 surface ligands

2016 ◽  
Vol 52 (12) ◽  
pp. 2577-2580 ◽  
Author(s):  
Farhan Ahmad Pasha ◽  
Anissa Bendjeriou-Sedjerari ◽  
Edy Abou-Hamad ◽  
Kuo-Wei Huang ◽  
Jean-Marie Basset
Keyword(s):  
Density Functional Theory ◽  
Solid State ◽  
Solid State Nmr ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Co2 Activation ◽  
Functional Theory ◽  
Surface Ligands ◽  
Different Types ◽  
Zirconium Hydrides

Density functional theory calculations and 2D 1H–13C HETCOR solid state NMR spectroscopy prove that CO2 can be used to probe, by its own reactivity, different types of N-donor surface ligands on SBA15-supported ZrIV hydrides: [(Si–O–)(Si–N)[Zr]H] and [(Si–NH–)(Si–X–)[Zr]H2] (XO or NH).

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