scholarly journals The Face-to-Face σ-Hole···σ-Hole Stacking Interactions: Structures, Energies, and Nature

Crystals ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 877
Author(s):  
Yu Zhang ◽  
Weizhou Wang
Keyword(s):  
Quantum Chemical ◽  
Noncovalent Interactions ◽  
Electrostatic Energy ◽  
Stacking Interactions ◽  
Energy Component ◽  
Stacking Interaction ◽  
Face To Face ◽  
The Face ◽  
Π Stacking Interaction ◽  
Induction Energy

The existence of the π···π stacking interaction is well-known. Similarly, it is reasonable to assume the existence of the σ-hole···σ-hole stacking interaction. In this work, the structures, energies, and nature of the face-to-face σ-hole···σ-hole stacking interactions in the crystal structures have been investigated in detail by the quantum chemical calculations. The calculated results clearly show that the face-to-face σ-hole···σ-hole stacking interactions exist and have unique properties, although their strengths are not very significant. The energy component analysis reveals that, unlike many other dispersion-dominated noncovalent interactions in which the induction energies always play minor roles for their stabilities, for the face-to-face σ-hole···σ-hole stacking interaction the contribution of the induction energy to the total attractive energy is close to or even larger than that of the electrostatic energy. The structures, energies, and nature of the face-to-face σ-hole···σ-hole stacking interactions confined in small spaces have also been theoretically simulated. One of the important findings is that encapsulation of the complex bound by the face-to-face σ-hole···σ-hole stacking interaction can tune the electronic properties of the container.

scholarly journals Noncovalent Interactions between 1,3,5-Trifluoro-2,4,6-triiodobenzene and a Series of 1,10-Phenanthroline Derivatives: A Combined Theoretical and Experimental Study

Crystals ◽  
2019 ◽  
Vol 9 (3) ◽  
pp. 140 ◽  
Author(s):  
Yu Zhang ◽  
Jian-Ge Wang ◽  
Weizhou Wang
Keyword(s):  
Crystal Structure ◽  
Crystal Structures ◽  
Quantum Chemical ◽  
Halogen Bond ◽  
Noncovalent Interactions ◽  
Stacking Interactions ◽  
Halogen Bonds ◽  
Π Stacking ◽  
Π Stacking Interaction ◽  
Structural Competition

How many strong C−I⋯N halogen bonds can one 1,3,5-trifluoro-2,4,6-triiodobenzene molecule form in a crystal structure? To answer this question, we investigated in detail the noncovalent interactions between 1,3,5-trifluoro-2,4,6-triiodobenzene and a series of 1,10-phenanthroline derivatives by employing a combined theoretical and experimental method. The results of the quantum chemical calculations and crystallographic experiments clearly show that there is a structural competition between a C−I⋯N halogen bond and π⋯π stacking interaction. For example, when there are much stronger π⋯π stacking interactions between two 1,10-phenanthroline derivative molecules or between two 1,3,5-trifluoro-2,4,6-triiodobenzene molecules in the crystal structures, then one 1,3,5-trifluoro-2,4,6-triiodobenzene molecule forms only one C−I⋯N halogen bond with one 1,10-phenanthroline derivative molecule. Another example is when π⋯π stacking interactions in the crystal structures are not much stronger, one 1,3,5-trifluoro-2,4,6-triiodobenzene molecule can form two C−I⋯N halogen bonds with two 1,10-phenanthroline derivative molecules.

scholarly journals Experimental and theoretical insights in the alkene–arene intramolecular π-stacking interaction

2016 ◽  
Vol 12 ◽  
pp. 1616-1623 ◽  
Author(s):  
Valeria Corne ◽  
Ariel M Sarotti ◽  
Carmen Ramirez de Arellano ◽  
Rolando A Spanevello ◽  
Alejandra G Suárez
Keyword(s):  
Electron Density ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Stacking Interactions ◽  
Nmr Studies ◽  
Stacking Interaction ◽  
Π Stacking ◽  
Acrylic Esters ◽  
Π Stacking Interaction

Chiral acrylic esters derived from biomass were developed as models to have a better insight in the aryl–vinyl π-stacking interactions. Quantum chemical calculations, NMR studies and experimental evidences demonstrated the presence of equilibriums of at least four different conformations: π-stacked and face-to-edge, each of them in an s-cis/s-trans conformation. The results show that the stabilization produced by the π–π interaction makes the π-stacked conformation predominant in solution and this stabilization is slightly affected by the electron density of the aromatic counterpart.

Long-Living Emitting Electrochemical Cells Based on Supramolecular π-π Interactions

2009 ◽  
Vol 1197 ◽  
Author(s):  
Rubén D. Costa ◽  
Enrique Ortí ◽  
Stefan Graber ◽  
Markus Neuburger ◽  
Catherine E. Hausecroft ◽  
...  
Keyword(s):  
Electrochemical Cells ◽  
Stacking Interactions ◽  
Light Emitting ◽  
Stacking Interaction ◽  
Face To Face ◽  
Π Interactions ◽  
Π Stacking ◽  
Π Stacking Interaction

AbstractThe complex [Ir(ppy)2(dpbpy)][PF6] (Hppy = 2-phenylpyridine, dpbpy = 6,6'-diphenyl-2,2'-bipyridine) has been prepared and evaluated as an electroluminescent component for light-emitting electrochemical cells (LECs). The complex exhibits two intramolecular face-to-face π-stacking interactions and long-lived LECs have been constructed; the device characteristics are not significantly improved in comparison to analogous LECs with 6-phenyl-2,2'-bipyridine with only one π-stacking interaction.

scholarly journals Strong stacking interactions of metal–chelate rings are caused by substantial electrostatic component

2019 ◽  
Vol 48 (19) ◽  
pp. 6328-6332 ◽  
Author(s):  
Dušan P. Malenov ◽  
Snežana D. Zarić
Keyword(s):  
Metal Chelate ◽  
Electrostatic Energy ◽  
Stacking Interactions ◽  
Energy Component ◽  
Electrostatic Component ◽  
Chelate Rings

Stacking interactions of metal–chelate rings are strong due to very strong electrostatic energy component.

scholarly journals Isomers and polymorphs of (E,E)-1,4-bis(nitrophenyl)-2,3-diaza-1,3-butadienes

2006 ◽  
Vol 62 (4) ◽  
pp. 666-675 ◽  
Author(s):  
Christopher Glidewell ◽  
John N. Low ◽  
Janet M. S. Skakle ◽  
James L. Wardell
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Stacking Interactions ◽  
Space Group ◽  
Stacking Interaction ◽  
Space Groups ◽  
Π Stacking ◽  
Π Stacking Interaction ◽  
Polymorphic Forms

The structures of five of the possible six isomers of (E,E)-1,4-bis(nitrophenyl)-2,3-diaza-1,3-butadiene are reported, including two polymorphs of one of the isomers. (E,E)-1,4-Bis(2-nitrophenyl)-2,3-diaza-1,3-butadiene, C14H10N4O4 (I), crystallizes in two polymorphic forms (Ia) and (Ib) in which the molecules lie across centres of inversion in space groups P21/n and P21/c, respectively: the molecules in (Ia) and (Ib) are linked into chains by aromatic π...π stacking interactions and C—H...π(arene) hydrogen bonds, respectively. Molecules of (E,E)-1-(2-nitrophenyl)-4-(3-nitrophenyl)-2,3-diaza-1,3-butadiene (II) are linked into sheets by two independent C—H...O hydrogen bonds. The molecules of (E,E)-1,4-bis(3-nitrophenyl)-2,3-diaza-1,3-butadiene (III) lie across inversion centres in the space group P21/n, and a combination of a C—H...O hydrogen bond and a π...π stacking interaction links the molecules into sheets. A total of four independent C—H...O hydrogen bonds link the molecules of (E,E)-1-(3-nitrophenyl)-4-(4-nitrophenyl)-2,3-diaza-1,3-butadiene (IV) into sheets. In (E,E)-1,4-bis(4-nitrophenyl)-2,3-diaza-1,3-butadiene (V) the molecules, which lie across centres of inversion in the space group P21/n, are linked by just two independent C—H...O hydrogen bonds into a three-dimensional framework.

scholarly journals Cooperative spin-crossover transition from three-dimensional purely π-stacking interactions in a neutral heteroleptic azobisphenolate FeIII complex with a N3O3 coordination sphere

2017 ◽  
Vol 46 (18) ◽  
pp. 5786-5789 ◽  
Author(s):  
Suguru Murata ◽  
Kazuyuki Takahashi ◽  
Tomoyuki Mochida ◽  
Takahiro Sakurai ◽  
Hitoshi Ohta ◽  
...  
Keyword(s):  
Coordination Sphere ◽  
Spin Crossover ◽  
Three Dimensional ◽  
Interaction Network ◽  
Stacking Interactions ◽  
Stacking Interaction ◽  
Π Stacking ◽  
Π Stacking Interaction ◽  
Crossover Transition ◽  
Cooperative Transition

The first neutral spin-crossover FeIII complex with a N3O3 coordination sphere formed a purely π-stacking interaction network and exhibited the cooperative transition.

Converting SMILES to Stacking Interaction Energies

2019 ◽  
Author(s):  
Andrea N. Bootsma ◽  
Steven Wheeler
Keyword(s):  
Quantum Chemical ◽  
Density Functional ◽  
Computational Cost ◽  
Aromatic Amino Acids ◽  
Stacking Interactions ◽  
Interaction Energies ◽  
Structure Based Drug Design ◽  
Stacking Interaction ◽  
Large Sets ◽  
Quantum Chemical Computations

<p>Predicting the strength of stacking interactions involving heterocycles is vital for several fields, including structure-based drug design. While quantum chemical computations can provide accurate stacking interaction energies, these come at a steep computational cost. To address this challenge, we recently developed quantitative predictive models of stacking interactions between drug-like heterocycles and the aromatic amino acids Phe, Tyr, and Trp (DOI: 10.26434/chemrxiv.7628939.v4). These models depend on heterocycle descriptors derived from electrostatic potentials (ESPs) computed using density functional theory and provide accurate stacking interactions without the need for expensive computations on stacked dimers. Herein, we show that these ESP-based descriptors can be reliably evaluated directly from the atom connectivity of the heterocycle, providing a means of predicting both the descriptors and the potential for a given heterocycle to engage in stacking interactions without resorting to any quantum chemical computations. This enables the conversion of simple molecular representations (<i>e.g</i>. SMILES) directly into accurate<i> </i>stacking interaction energies using a freely-available online tool, thereby providing a way to rapidly rank the stacking abilities of large sets of heterocycles.</p> <p> </p>

scholarly journals Converting SMILES to Stacking Interaction Energies

2019 ◽  
Author(s):  
Andrea N. Bootsma ◽  
Steven Wheeler
Keyword(s):  
Quantum Chemical ◽  
Density Functional ◽  
Computational Cost ◽  
Aromatic Amino Acids ◽  
Stacking Interactions ◽  
Interaction Energies ◽  
Structure Based Drug Design ◽  
Stacking Interaction ◽  
Large Sets ◽  
Quantum Chemical Computations

<p>Predicting the strength of stacking interactions involving heterocycles is vital for several fields, including structure-based drug design. While quantum chemical computations can provide accurate stacking interaction energies, these come at a steep computational cost. To address this challenge, we recently developed quantitative predictive models of stacking interactions between drug-like heterocycles and the aromatic amino acids Phe, Tyr, and Trp (DOI: 10.26434/chemrxiv.7628939.v4). These models depend on heterocycle descriptors derived from electrostatic potentials (ESPs) computed using density functional theory and provide accurate stacking interactions without the need for expensive computations on stacked dimers. Herein, we show that these ESP-based descriptors can be reliably evaluated directly from the atom connectivity of the heterocycle, providing a means of predicting both the descriptors and the potential for a given heterocycle to engage in stacking interactions without resorting to any quantum chemical computations. This enables the conversion of simple molecular representations (<i>e.g</i>. SMILES) directly into accurate<i> </i>stacking interaction energies using a freely-available online tool, thereby providing a way to rapidly rank the stacking abilities of large sets of heterocycles.</p> <p> </p>

Hydrogen-bonded sheet structures in methyl 4-(4-chloroanilino)-3-nitrobenzoate and methyl 1-benzyl-2-(4-chlorophenyl)-1H-benzimidazole-5-carboxylate

2012 ◽  
Vol 69 (1) ◽  
pp. 77-81
Author(s):  
Edwar Cortés ◽  
Rodrigo Abonía ◽  
Justo Cobo ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Stacking Interactions ◽  
Electronic Polarization ◽  
Stacking Interaction ◽  
Π Stacking ◽  
Π Stacking Interaction ◽  
Hydrogen Bonded

In methyl 4-(4-chloroanilino)-3-nitrobenzoate, C14H11ClN2O4, (I), there is an intramolecular N—H...O hydrogen bond and the intramolecular distances provide evidence for electronic polarization of theo-quinonoid type. The molecules are linked into sheets built from N—H...O, C—H...O and C—H...π(arene) hydrogen bonds, together with an aromatic π–π stacking interaction. The molecules of methyl 1-benzyl-2-(4-chlorophenyl)-1H-benzimidazole-5-carboxylate, C22H17ClN2O2, (II), are also linked into sheets, this time by a combination of C—H...π(arene) hydrogen bonds and aromatic π–π stacking interactions.

scholarly journals A Robust Supramolecular Heterosynthon Assembled by a Hydrogen Bond and a Chalcogen Bond

Crystals ◽  
2021 ◽  
Vol 11 (11) ◽  
pp. 1309
Author(s):  
Shaobin Miao ◽  
Yunfan Zhang ◽  
Linjie Shan ◽  
Mingyuan Xu ◽  
Jian-Ge Wang ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bond ◽  
Crystal Structures ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Noncovalent Interactions ◽  
Isophthalic Acid ◽  
Stacking Interactions ◽  
Chalcogen Bond ◽  
Good Agreement

The 1:1 and 2:1 cocrystals of isophthalic acid and 2,1,3-benzoselenadiazole have been successfully synthesized and resolved; the noncovalent interactions in the crystal structures have been studied in detail by quantum chemical calculations. In both of the crystal structures, isophthalic acid and 2,1,3-benzoselenadiazole are bound together by a cyclic supramolecular heterosynthon assembled by an O–H···N hydrogen bond and a N–Se···O chalcogen bond. The crystal structures of the 1:1 and 2:1 cocrystals of isophthalic acid and 2,1,3-benzoselenadiazole and the crystal structure of pure isophthalic acid are very similar, which indicates that the [COOH]···[Se−N] cyclic heterosynthon can be an effective alternative to the strong [COOH]2 cyclic homosynthon. The quantum theory of atoms in molecules further recognizes the existence of the hydrogen bond and chalcogen bond. The results of quantum chemical calculations show that the strengths of the π···π stacking interactions in the 1:1 cocrystals of isophthalic acid and 2,1,3-benzoselenadiazole are almost the same as those in the 2:1 cocrystals of isophthalic acid and 2,1,3-benzoselenadiazole, and the strengths of the [COOH]···[Se−N] cyclic heterosynthons (about 9.00 kcal/mol) are less than the strengths of the much stronger [COOH]2 cyclic homosynthons (14.00 kcal/mol). These calculated results are in good agreement with those experimentally observed, demonstrating that, although not as strong as the [COOH]2 cyclic homosynthon, the [COOH]···[Se−N] cyclic heterosynthon can also play a key role in the crystal growth and design.

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