scholarly journals “Anti-Electrostatic” Halogen Bonding

2020 ◽  
Author(s):  
Jana Holthoff ◽  
Elric Engelage ◽  
Robert Weiss ◽  
Stefan Huber
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Gas Phase ◽  
Electrostatic Potential ◽  
Lewis Acids ◽  
Halogen Bonding ◽  
Halide Complexes ◽  
Self Association ◽  
Solid State Structures ◽  
Van Der Waals Radii

Halogen bonding (XB) is often described as being driven predominantly by electrostatics, and thus adducts between <i>anionic</i> XB donors (halogen-based Lewis acids) and anions seem counter­intuitive. Such “anti-electrostatic” XBs have been predicted theoretically, but there are currently no experimental examples based on organic XB donors. Herein, we report the synthesis of two negatively charged organoiodine derivatives, which were subsequently investigated towards their ability to form “anti-electrostatic” XBs with anions. Even though the electrostatic potential is universally negative across the surface of both compounds, DFT calculations indicate kinetic stabilization of their halide complexes in the gas phase and particularly in solution. Experimentally, self-association of the anionic XB donors was observed in solid-state structures, resulting in dimers, trimers and infinite chains. In addition, co-crystals with halides were obtained which featured XB adducts between two or even three anions. The bond-lengths of all observed interactions are 14-21% shorter than sum of the van-der-Waals radii.

scholarly journals “Anti-Electrostatic” Halogen Bonding

2020 ◽  
Author(s):  
Jana Holthoff ◽  
Elric Engelage ◽  
Robert Weiss ◽  
Stefan Huber
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Gas Phase ◽  
Electrostatic Potential ◽  
Lewis Acids ◽  
Halogen Bonding ◽  
Halide Complexes ◽  
Self Association ◽  
Solid State Structures ◽  
Van Der Waals Radii

Halogen bonding (XB) is often described as being driven predominantly by electrostatics, and thus adducts between <i>anionic</i> XB donors (halogen-based Lewis acids) and anions seem counter­intuitive. Such “anti-electrostatic” XBs have been predicted theoretically, but there are currently no experimental examples based on organic XB donors. Herein, we report the synthesis of two negatively charged organoiodine derivatives, which were subsequently investigated towards their ability to form “anti-electrostatic” XBs with anions. Even though the electrostatic potential is universally negative across the surface of both compounds, DFT calculations indicate kinetic stabilization of their halide complexes in the gas phase and particularly in solution. Experimentally, self-association of the anionic XB donors was observed in solid-state structures, resulting in dimers, trimers and infinite chains. In addition, co-crystals with halides were obtained which featured XB adducts between two or even three anions. The bond-lengths of all observed interactions are 14-21% shorter than sum of the van-der-Waals radii.

σ-Hole halogen bonding interactions in a mixed valence cobalt(iii/ii) complex and anti-electrostatic hydrogen bonding interaction in a cobalt(iii) complex: a theoretical insight

CrystEngComm ◽  
2018 ◽  
Vol 20 (45) ◽  
pp. 7281-7292 ◽  
Author(s):  
Kousik Ghosh ◽  
Klaus Harms ◽  
Antonio Bauzá ◽  
Antonio Frontera ◽  
Shouvik Chattopadhyay
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Dft Calculations ◽  
Mixed Valence ◽  
Halogen Bonding ◽  
Supramolecular Interactions ◽  
Hydrogen Bonding Interaction ◽  
Bonding Interaction ◽  
Solid State Structures ◽  
Theoretical Insight

Supramolecular interactions in the solid state structures of a mixed valence cobalt(ii/iii) complex and a cobalt(iii) complex have been studied using DFT calculations.

scholarly journals Inter- and Intramolecular Aryl-Aryl-Interactions in Partially Fluorinated Ethylenedioxy-Bridged Bisarenes

2020 ◽  
Author(s):  
Jan-Henrik Weddeling ◽  
Yury Vishnevskiy ◽  
Beate Neumann ◽  
Hans-Georg Stammler ◽  
Norbert W. Mitzel
Keyword(s):  
Solid State ◽  
Electron Diffraction ◽  
Dft Calculations ◽  
Gas Phase ◽  
Single Molecule ◽  
Structure Refinement ◽  
Intramolecular Interactions ◽  
Gas Electron Diffraction ◽  
Dispersion Energy ◽  
Solid State Structures

Several ethylenedioxy-bridged bisarenes with a variety of type and number of aryl groups were synthesized to study non-covalent dispersion-driven inter- and intramolecular aryl-aryl-interactions in the solid state and gas phase. Intramolecular interactions are preferably found in the gas phase. DFT calculations of dispersion-corrected energy scans for rotations around the ethylenedioxy-bridge and optimized structures show larger interacting aromatic groups to increase the dispersion energy. Single molecule structures generally adopt folded conformations with short intramolecular aryl-aryl-contacts. Gas electron diffraction experiments were performed exemplarily for 1-(pentafluorophenoxy)-2-(phenoxy)ethane. A new procedure for structure refinement was developed to deal with the conformational complexity of such molecules. The results are an experimental confirmation of the existence of folded conformations of this molecule with short -intramolecular aryl-aryl distances in the gas phase. Solid-state structures are dominated by stretched structures without intramolecular aryl-aryl-interactions but interactions with neighboring molecules<br>

scholarly journals Inter- and Intramolecular Aryl-Aryl-Interactions in Partially Fluorinated Ethylenedioxy-Bridged Bisarenes

2020 ◽  
Author(s):  
Jan-Henrik Weddeling ◽  
Yury Vishnevskiy ◽  
Beate Neumann ◽  
Hans-Georg Stammler ◽  
Norbert W. Mitzel
Keyword(s):  
Solid State ◽  
Electron Diffraction ◽  
Dft Calculations ◽  
Gas Phase ◽  
Single Molecule ◽  
Structure Refinement ◽  
Intramolecular Interactions ◽  
Gas Electron Diffraction ◽  
Dispersion Energy ◽  
Solid State Structures

Several ethylenedioxy-bridged bisarenes with a variety of type and number of aryl groups were synthesized to study non-covalent dispersion-driven inter- and intramolecular aryl-aryl-interactions in the solid state and gas phase. Intramolecular interactions are preferably found in the gas phase. DFT calculations of dispersion-corrected energy scans for rotations around the ethylenedioxy-bridge and optimized structures show larger interacting aromatic groups to increase the dispersion energy. Single molecule structures generally adopt folded conformations with short intramolecular aryl-aryl-contacts. Gas electron diffraction experiments were performed exemplarily for 1-(pentafluorophenoxy)-2-(phenoxy)ethane. A new procedure for structure refinement was developed to deal with the conformational complexity of such molecules. The results are an experimental confirmation of the existence of folded conformations of this molecule with short -intramolecular aryl-aryl distances in the gas phase. Solid-state structures are dominated by stretched structures without intramolecular aryl-aryl-interactions but interactions with neighboring molecules<br>

scholarly journals Zn(II) Heteroleptic Halide Complexes with 2-Halopyridines: Features of Halogen Bonding in Solid State

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3393
Author(s):  
Mikhail A. Vershinin ◽  
Marianna I. Rakhmanova ◽  
Alexander S. Novikov ◽  
Maxim N. Sokolov ◽  
Sergey A. Adonin
Keyword(s):  
Solid State ◽  
Quantum Yield ◽  
Crystal Packing ◽  
Halogen Bonding ◽  
Molecular Complexes ◽  
Substituted Pyridines ◽  
Halide Complexes

Reactions between Zn(II) dihalides and 2-halogen-substituted pyridines 2-XPy result in a series of heteroleptic molecular complexes [(2-XPy)2ZnY2] (Y = Cl, X = Cl (1), Br (2), I (3); Y = Br, X = Cl (4), Br (5), I (6), Y = I, X = Cl (7), Br (8), and I (9)). Moreover, 1–7 are isostructural (triclinic), while 8 and 9 are monoclinic. In all cases, halogen bonding plays an important role in formation of crystal packing. Moreover, 1–9 demonstrate luminescence in asolid state; for the best emitting complexes, quantum yield (QY) exceeds 21%.

scholarly journals Fluorinated azobenzenes as supramolecular halogen-bonding building blocks

2019 ◽  
Vol 15 ◽  
pp. 2013-2019 ◽  
Author(s):  
Esther Nieland ◽  
Oliver Weingart ◽  
Bernd M Schmidt
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Visible Light ◽  
Half Life ◽  
Photophysical Properties ◽  
Bathochromic Shift ◽  
Halogen Bonding ◽  
Building Blocks ◽  
Partial Overlap

ortho-Fluoroazobenzenes are a remarkable example of bistable photoswitches, addressable by visible light. Symmetrical, highly fluorinated azobenzenes bearing an iodine substituent in para-position were shown to be suitable supramolecular building blocks both in solution and in the solid state in combination with neutral halogen bonding acceptors, such as lutidines. Therefore, we investigate the photochemistry of a series of azobenzene photoswitches. Upon introduction of iodoethynyl groups, the halogen bonding donor properties are significantly strengthened in solution. However, the bathochromic shift of the π→π* band leads to a partial overlap with the n→π* band, making it slightly more difficult to address. The introduction of iodine substituents is furthermore accompanied with a diminishing thermal half-life. A series of three azobenzenes with different halogen bonding donor properties are discussed in relation to their changing photophysical properties, rationalized by DFT calculations.

Intramolecular London Dispersion Interaction Effects on Gas-Phase and Solid-State Structures of Diamondoid Dimers

2017 ◽  
Vol 139 (46) ◽  
pp. 16696-16707 ◽  
Author(s):  
Andrey A. Fokin ◽  
Tatyana S. Zhuk ◽  
Sebastian Blomeyer ◽  
Cristóbal Pérez ◽  
Lesya V. Chernish ◽  
...  
Keyword(s):  
Solid State ◽  
Gas Phase ◽  
Interaction Effects ◽  
Dispersion Interaction ◽  
London Dispersion ◽  
Solid State Structures

The solid state structures of the high and low temperature phases of dimethylcadmium

2016 ◽  
Vol 52 (66) ◽  
pp. 10144-10146 ◽  
Author(s):  
Felix Hanke ◽  
Sarah Hindley ◽  
Anthony C. Jones ◽  
Alexander Steiner
Keyword(s):  
Solid State ◽  
Low Temperature ◽  
Dft Calculations ◽  
Methyl Groups ◽  
X Ray ◽  
Solid State Structures

X-ray structures and DFT calculations show that the HT phase is of Me2Cd is two-dimensionally disordered, while the LT phase is ordered. Both phases contain linearly coordinated cadmium atoms; methyl groups are staggered in the HT form and eclipsed in the LT-form.

Synthesis of a bifunctional boron-Lewis acid and studies on host-guest chemistry using pyridine and TMPD

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Jens Rudlof ◽  
Beate Neumann ◽  
Hans-Georg Stammler ◽  
Norbert W. Mitzel
Keyword(s):  
Solid State ◽  
Lewis Acid ◽  
Lewis Acids ◽  
Structure Elucidation ◽  
Decomposition Product ◽  
Functional Distance ◽  
Solid State Structures ◽  
Guest Chemistry

Abstract Based on the previously described bifunctional Lewis acid with a functional distance of the boron functions of 4.918(2) Å, the development of a further bifunctional, boron-containing Lewis acid with a wider functional distance is demonstrated. Again, a stannylated precursor was used and the Lewis-acidic boron functions were introduced by means of tin-boron exchange. The general suitability of this class of compounds for the formation of host-guest-complexes is demonstrated by NMR experiments and by solid-state structures using pyridine and TMPD (N 1,N 1,N 4,N 4-tetramethylbenzene-1,4-diamine) as Lewis basic guests. The influence of traces of moisture on the boron-containing, bifunctional Lewis acids was investigated by the structure elucidation of a decomposition product.

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