Fig 1 - available via license: Creative Commons Attribution-NonCommercial 3.0 Unported
Content may be subject to copyright.
Electrostatic potential maps for the electrostatic positive regions of monomers on the 0.001 a.u. isodensity surface with potentials ranging from À12 kcal mol À1 (red) to 12 kcal mol À1 (blue). All energy values are reported in kcal mol À1 .
Source publication
In this article, the existence of NO noncovalent interactions was explored in per-halo substituted ammonia-water complexes. Optimized geometry at the MP2/aug-cc-pVTZ level shows that the NO distance in all complexes is less than the sum of the vdW radii of N and O. The strength of these contacts was directly dependent on the extent of chlorine subs...
Similar publications
The synthesis of gold(III) and gold(I)–gold(III) complexes with phosphide bridges is still a matter that requires solutions for their marked instability, in spite of the affinity of this metal in both oxidation states for phosphorous donor ligands. In the course of our studies, we realized that the presence of perhalophenyl groups of the type penta...
- [...]
The complexes formed between MgX2 (X = F, H) molecules and alkyl radicals Y [Y = CH3, CH2CH3, CH(CH3)2, and C(CH3)3] have been characterized by using quantum chemical methods. The binding distance in all cases is less than the sum of vdW radii of Mg and C, indicating the formation of a non-covalent interaction, namely single-electron magnesium bond...
Aromatic stacking interactions have been a matter of study and debate due to their crucial role in chemical and biological systems. The strong dependence on orientation and solvent together with the relatively small interaction energies have made evaluation and rationalization a challenge for experimental and theoretical chemists. We have used a su...
Based on the data obtained by molecular modeling of the non-covalent interaction of non-symmetric N-benzylbispidin-9-ol amides with the active site of the main protease 3CLpro of the SARS-CoV-2 virus, a series of compounds was synthesized, and their inhibitory activity against 3CLpro was studied and compared with that of the known inhibitor ML188 (...
Anthracene-9,10-dicarboxaldehyde (ADCA) is a polynuclear aromatic compound that has a planar structure with double bonds which are in conjugation. The molecule is subjected to theoretical investigation with DFT/B3LYP/6-311++G(d,p) basis set to find out the electronic structural properties and stability. Theoretical and experimental vibrational anal...
Citations
... The infrared absorption and Raman scattering observables of both R-Pn and A are affected by PnB formation; the vibrational frequency of the R-Pn bond may be redshifted or blue-shifted depending on the extent of the interactions involved compared to the frequency of the same bond in the isolated molecular entity; new vibrational modes associated with the formation of the Pn···A intermolecular pnictogen bond should also be characteristically observed [116,117], as observed for ChBs; g. A bond path and a bond-critical point between Pn and A may be found when an electron density topology analysis based on the quantum theory of atoms in molecules (QTAIM) [118] is carried out, together with the emergence of other charge density-based signatures [119][120][121][122][123]; h. Isosurface volumes (colored greenish, blue, or mixed blue-green between Pn and A, representative of attractive interactions [6,7,[11][12][13]124]) may be seen if a non-covalent index analysis based on reduced charge density gradient [125][126][127] is performed; i. ...
This article proposes a definition for the term pnictogen bond and lists its donors, acceptors, and characteristic features. These may be invoked to identify this specific subset of the inter- and intra-molecular interactions formed by elements of Group 15 which possess an electrophilic site in a molecular entity.
... A bond path and a bond-critical point between Pn and A may be found when an electron density topology analysis based on the quantum theory of atoms in molecules (QTAIM) [118] is carried out, together with the emergence of other charge density-based signatures [119][120][121][122][123]; h. ...
This article proposes a definition for the term “pnictogen bond” and lists its donors, acceptors, and characteristic features. These may be invoked to identify this specific subset of the inter- and intramolecular interactions formed by elements of Group 15 which possess an electrophilic site in a molecular entity.
... Many works describing G-15 NCIs theoretically are available in the literature (43,44,(112)(113)(114)(115)(116)(117)(118)(119), but those describing experimental evidence are less frequent (120)(121)(122)(123). It has been recently used in supramolecular catalyst (124) and crystal engineering (43,44,125). ...
Elements belonging to Groups 14–17 and Periods 3–6 frequently act as Lewis acids which are able to establish directional noncovalent interactions (NCI) with a variety of Lewis bases (lone pair donors), π-systems (aromatic rings, triple and double bonds) and non-nucleophilic anions (BF4–, PF6–, ClO4–, etc.). These promising NCIs are named in general as σ-hole interactions that are subdivided as tetrel bonds for elements belonging to group 14, pnictogen bonding for group 15, chalcogen bonding for group 16, and halogen bonding for group 17. In general, σ-hole interactions offer differentiating features when moving down in the same group (larger and more positive σ-holes) or moving left in the same row (number of available σ-holes and directionality) of the periodic table. This chapter shows that Molecular Electrostatic Potential (MEP) surface calculation is a powerful tool to explain the solid-state architecture of many X-ray structures. This is exemplified by using many examples retrieved from the Cambridge Structural Database (CSD), especially focused on σ-hole interactions.
... ;i. the infrared absorption and Raman scattering observables of both R-Tt and A are affected by TtB formation; the vibrational frequency of the R-Tt bond in the isolated molecular entity; new vibrational modes associated with the formation of the Tt···A intermolecular pnictogen bond should also be characteristically observed, as for HBs, XBs and CBs; j. the NMR chemical shifts of nuclei in both R-Tt and A are typically affected (with the former increased or decreased[101]), as found for R-X···A XBs and R-Ch···A ChBs[18,[104][105][106][107]; the isotropic coupling constant of the TtB donor may tend to decrease relative to that of the isolated TtB donor[25,108], as observed for HBs and XBs[109]; k. the UV-vis absorption bands of the TtB donor chromophore may experience shift to longer wavelengths; l. a bond path and a bond critical point between TtB donor atom Tt and A may be found when an electron density topology analysis based on the quantum theory of atoms in molecules (QTAIM)[110] theory is carried out, together with other charge density-based signatures[111][112][113][114][115]; m. isosurface volumes (may be colored in greenish, blue, or mixed blue-green between TtB donor atom Tt and A, representative of attractive interactions[58,[97][98][99][100]116]), may be seen if a non-covalent index analysis based on reduced density gradients[117][118][119] is performed; similar isosurface features may also emerge when an independent gradient model (IGM)[118,119] or an IGM based on Hirshfeld partition of molecular density (IGMH)[120], or an Interaction Region Indicator (IRI)[121,122], analysis is performed; n. at least some transfer of charge density from the frontier TtB acceptor orbital to frontier TtB donor orbital may occur[102,123,124]; when the transfer of electron charge density between them is significant, the formation of a dative interaction is likely[102]; the occurrence of the phenomena IUPAC recommended for HBs (see Criteria E1 and Characteristic C5 of Ref.[1]) is also applicable to XBs[125][126][127][128] and ChBs[129][130][131], and PnBs[4,132,133];o. the nature of charge-transfer delocalization between Lewis-type frontier TtB donor and acceptor orbitals causing formation of a tetrel bond may be quantified by a second-order perturbation theory analysis of the Fock matrix of the Natural Bond Orbital (NBO) involved[141][142][143].p. the tetrel bond strength typically increases with a given TtB acceptor A, as the electronegativity of Tt decreases in the order C > Si > Ge > Sn > Pb and the electron withdrawing ability of R increases[12,18,107,134]; ...
This article proposes a definition of the term "Tetrel bond". It lists the donors, acceptors, and related characteristic features of tetrel bonds that are commonly observed in the crystalline phase and/or that emerge from first principles calculations in the solid-state and gas phases. These may be used to identify, characterize and classify the unique subset of inter- and intra-molecular interactions formed by elements of Group 14 of the Periodic Table that possess an electrophilic site in a molecular entity.
... A great deal of studies dealing with PnBs are already available in the literature [43,44,[75][76][77][78][79][80][81][82][83][84][85]. However, those presenting experimental evidence of the interaction are scarce [86][87][88][89]. ...
In this review, several examples of the application of pnictogen (Pn) (group 15) and chalcogen (Ch) bonding (group 16) interactions in organocatalytic processes are gathered, backed up with Molecular Electrostatic Potential surfaces of model systems. Despite the fact that the use of catalysts based on pnictogen and chalcogen bonding interactions is taking its first steps, it should be considered and used by the scientific community as a novel, promising tool in the field of organocatalysis.
... A plethora of theoretical works dealing with PnBs are available in the literature [43,44,[76][77][78][79][80][81][82][83]. However, those presenting experimental evidence are much less common [84][85][86][87][88][89]. Nevertheless, this interaction has been recently proposed for the design and synthesis of supramolecular catalysts by Matile et al. [90]. ...
Elements from groups 14-18 and periods 3-6 commonly behave as Lewis acids, which are involved in directional noncovalent interactions (NCI) with electron-rich species (lone pair donors), π systems (aromatic rings, triple and double bonds) as well as nonnucleophilic anions (BF4 − , PF6 − , ClO4 − , etc.). Moreover, elements of groups 15 to 17 are also able to act as Lewis bases (from one to three available lone pairs, respectively), thus presenting a dual character. These emerging NCIs where the main group element behaves as Lewis base, belong to the σ-hole family of interactions. Particularly (i) tetrel bonding for elements belonging to group 14, (ii) pnictogen bonding for group 15, (iii) chalcogen bonding for group 16, (iv) halogen bonding for group 17, and (v) noble gas bond-ings for group 18. In general, σ-hole interactions exhibit different features when moving along the same group (offering larger and more positive σ-holes) or the same row (presenting a different number of available σ-holes and directionality) of the periodic table. This is illustrated in this review by using several examples retrieved from the Cambridge Structural Database (CSD), especially fo-cused on σ-hole interactions, complemented with molecular electrostatic potential surfaces of model systems.
... The existence of nitrogen-centered N⋅⋅⋅Cl pnictogen bonding interaction was also confirmed from high-resolution X-ray charge density analysis 37 . In our previous study on chalcogen and pnictogen bonds, we examined the formation of N⋅⋅⋅O noncovalent interactions in XYZN:OXY systems (X/Y/Z = F/Cl), where we observed that these N⋅⋅⋅O interactions can be tuned to be a chalcogen bond or pnictogen bonding interaction, depending on the strength of the electron-withdrawing substituent attached directly to the interacting atoms 38 . Another ab initio study similarly established the formation of oxygen-centred chalcogenbonding interaction with different nucleophilic species 39 . ...
... While studies involving chalcogen or pnictogen, as either electrophile or nucleophile are present in abundance, there are interactions where chalcogen or pnictogen can simultaneously behave as an electron-donor and electron-acceptor in the formation of the same interaction. While the previously discussed N⋅⋅⋅O interactions were very weak and dispersive 38 , orbital analysis revealed that in some dimeric complexes, N⋅⋅⋅O interaction had simultaneous characteristics of both chalcogen as well as pnictogen bonding interactions. In another study, we analysed Se⋅⋅⋅P noncovalent interaction in XHSe : PH 3 , H 2 Se : PH 2 X and XHSe : PH 2 X dimers using ab initio calculations 42 . ...
... As shown in Fig. 2, there are two bond paths that are developed between the nitrogen outer surface and the coordinated bromides in o-MAPbBr 3 . These can be regarded as Br/NeC type s-hole centered pnictogen bonding [12,13,93,95]. These contacts are formed because the outer portion of the 0.001 au isoelectron density mapped electrostatic surface of nitrogen/carbon along the extension of the CeN/NeC s-bond in MA is found to be positive that attracts the negative site to form a non-covalent interaction. ...
Methylammonium lead tribromide (CH3NH3PbBr3) perovskite as a photovoltaic material has attracted a great deal of recent interest. Factors that are important in their application in optoelectronic devices include their fractional contribution of the composition of the materials as well as their microscopic arrangement that is responsible for the formation of well-defined macroscopic structures. CH3NH3PbBr3 assumes different polymorphs (orthorhombic, tetragonal and cubic) depending on the evolution temperature of the bulk material. An understanding of the structure of these compounds will assist in rationalizing how halogen-centered non-covalent interactions play an important role in the rational design of these materials. Density functional theory (DFT) calculations have been performed on polymorphs of CH3NH3PbBr3 to demonstrate that the H atoms on C of the methyl group in CH3NH3+ entrapped within a PbBr64− perovskite cage are not electronically innocent, as is often contended. We show here that these H atoms are involved in attractive interactions with the surrounding bromides of corner-sharing PbBr64− octahedra of the CH3NH3PbBr3 cage to form Br⋯H(C) hydrogen bonding interactions. This is analogous to the way the H atoms on N of the NH3+ group in CH3NH3+ form Br⋯H(N) hydrogen bonding interactions to stabilize the structure of CH3NH3PbBr3. Both these hydrogen bonding interactions are shown to persist regardless of the nature of the three polymorphic forms of CH3NH3PbBr3. These, together with the Br⋯C(N) carbon bonding, the Br⋯N(C) pnictogen bonding, and the Br⋯Br lump-hole type intermolecular non-covalent interactions identified for the first time in this study, are shown to be collectively responsible for the eventual emergence of the orthorhombic geometry of the CH3NH3PbBr3 system. These conclusions are arrived at from a systematic analysis of the results obtained from combined DFT, Quantum Theory of Atoms in Molecules (QTAIM), and Reduced Density Gradient Non-Covalent Interaction (RDG-NCI) calculations carried out on the three temperature-dependent polymorphic geometries of CH3NH3PbBr3.
... S3-S4.As shown inFigure 2, there are two bond paths that are developed between the nitrogen outer surface and the coordinated bromides in o-MAPbBr 3 . These can be regarded as Br⋯N-C type -hole centered pnictogen bonding[12,13,93,95]. These contacts are formed because the outer portion of the 0.001 au isoelectron density mapped electrostatic surface of nitrogen/carbon along the extension of the C-N/N-C -bond in MA is found to be positive that attracts the negative site to form a non-covalent interaction. ...
... There are many theoretical studies on chalcogen bonds [24][25][26][27][28][29][30][31][32]. Scheiner and Adhikari [33] have compared hydrogen and halogen bonds in S···N interactions in HSX:NH 3 (X = F, Cl, Br). ...
The S···P interactions in the complexes of HSX (X = F, Cl, Br, I) with PHnMe3-n(n = 0–3) have been investigated with ab initio calculations at the MP2/aug-cc-pVDZ and MP2/aug-cc-pVTZ//MP2/aug-cc-pVDZ level of theory. The interaction energies and structural properties of intermolecular complexes have been analyzed. Results of QTAIM analysis are dealing with expand of interactions, including pure closed-shell interactions (van der Waals interactions and chalcogen bonding, YB), partially covalent closed-shell (CS; Charge Transfer) and shared-shell interactions (SS; weak covalent bond and very strong YB) for these complexes. The energy decomposition analysis (EDA) showed that electrostatic interactions are an important contributing factor for these complexes. In considering second-order contributions, the donor-acceptor pair charge transfer (CT) is most important. These findings are consistent with the Electron Localization Function (ELF) isosurface of the complexes. In each series of HXS:PHnMe3-n-chalcogen bond complexes with increasing basicity of phosphines, the stability and S···P bond strength of adducts were increased so that the HXS:PMe3 (X = F, Cl, Br) complexes had very strong S···P chalcogen interactions with nearly covalent characters.
