Search results
Search for "dispersion interactions" in Full Text gives 31 result(s) in Beilstein Journal of Organic Chemistry.
Complexes of resorcin[4]arene with secondary amines: synthesis, solvent influence on “in-out” structure, and theoretical calculations of non-covalent interactions
Beilstein J. Org. Chem. 2023, 19, 1525–1536, doi:10.3762/bjoc.19.109
- exchange and dispersion interactions in CHCl3 in relation to DMSO are the driving forces behind the placement of sec-amine molecules into the R[4]A cavity and the formation of “in” type complexes. Keywords: complexes; DFT calculations; hydrogen bond; resorcin[4]arene; supramolecular chemistry
- DMSO. On the other hand, the dispersion interactions are about twice as high in CHCl3 compared to DMSO and increase with the size of the amine molecule. Their percentage value, however, is slightly lower than that of the exchange interactions and ranges from 2.8% to 11.1%. The smallest contribution to
- electrostatic interactions and the increase in exchange and dispersion interactions in CHCl3 compared to DMSO are the driving forces behind the placement of sec-amine molecules into the R[4]A cavity and the formation of “in”-type complexes. In the case of complexes with 1:2 stoichiometry, the shares of
A new oxidatively stable ligand for the chiral functionalization of amino acids in Ni(II)–Schiff base complexes
Beilstein J. Org. Chem. 2023, 19, 566–574, doi:10.3762/bjoc.19.41
- electrochemically induced oxidative modification of the amino acid side chain. Experimental and DFT studies showed that the additional tert-butyl group increases the dispersion interactions in the Ni coordination environment making the complexes more conformationally rigid and provides a higher level of
- give rise to additional dispersion interactions with the phenyl ring in the proline auxiliary, making the Schiff base complexes more conformationally rigid, thus increasing the stereochemical outcome of the functionalized amino acids as compared to the parent ligand L1. In the present paper, the new
- are presented in different colors: the hydrogen bonding are labeled in blue color of the reduced density gradient isosurface; green color corresponds to the dispersion interactions (van der Waals interactions, the π-stacking); red color represents steric clashes. The interplay of these through-space
Comparison of crystal structure and DFT calculations of triferrocenyl trithiophosphite’s conformance
Beilstein J. Org. Chem. 2022, 18, 1499–1504, doi:10.3762/bjoc.18.157
- describe the London dispersion interactions as implemented in the Gaussian 16 program. Results and Discussion Previous electrochemical studies for triferrocenyl trithiophosphite revealed in their cyclovoltammograms three reversible one-electron peaks corresponding to stepwise oxidation of the three
Understanding the competing pathways leading to hydropyrene and isoelisabethatriene
Beilstein J. Org. Chem. 2022, 18, 972–978, doi:10.3762/bjoc.18.97
- any free energy barrier. The deprotonation and re-protonation steps are not included in our calculations. The overall exergonicity of this process which transforms four π-bonds to σ-bonds, with accompanying gains in intramolecular dispersion interactions, is −62.8 kcal/mol. IE pathway As described
- carbocation A’ is significant, due to the exchange of two π-bonds for σ-bonds, as well as gain in dispersion interactions on folding of the extended geranylgeranyl cation. Discussion Although the current calculations were performed in the gas phase without inclusion of the enzyme environment, we may still
N-Sulfinylpyrrolidine-containing ureas and thioureas as bifunctional organocatalysts
Beilstein J. Org. Chem. 2021, 17, 2629–2641, doi:10.3762/bjoc.17.176
- -range London dispersion interactions. Geometrical optimizations were performed with the Karlsruhe split-valence def2-SV(P) basis set [41]. Energies were refined using the Minnesota M06-2X functional [42] and valence triple-zeta def2-TZVP basis set [43]. The lowest energy conformers of both catalyst (S,R
Tuning the solid-state emission of liquid crystalline nitro-cyanostilbene by halogen bonding
Beilstein J. Org. Chem. 2021, 17, 124–131, doi:10.3762/bjoc.17.13
- temperature, which indicates that the strength of the halogen bond is not the only contributor to the mesomorphic behaviour of the halogen-bonded materials. The change in the electronic anisotropy by unsymmetrical substitution with fluorine as present in F3Az will also have an impact on the dispersion
- interactions and packing in the solid state and adds to the shift of the crystallisation temperature. Photophysical studies Recently, our group has shown that self-assembly provides an efficient way to tune fluorescence behaviour of liquid crystalline materials [21]. Phenolic thioethers showing aggregation
Dirhamnolipid ester – formation of reverse wormlike micelles in a binary (primerless) system
Beilstein J. Org. Chem. 2020, 16, 2820–2830, doi:10.3762/bjoc.16.232
- Information File 1). Both values are identical and amount to ΔHGS,SG = ±7.2 kJ/mol, which is in the order of strong dispersion energies. This further proves the formation of network-like structures by the entanglement of RWLM due to attractive dispersion interactions between the alkyl chains of neighboring
Comparative ligand structural analytics illustrated on variably glycosylated MUC1 antigen–antibody binding
Beilstein J. Org. Chem. 2020, 16, 2540–2550, doi:10.3762/bjoc.16.206
- dispersion interactions would be insufficient to explain a 20-fold increase in affinity. It is unlikely that this hydrogen bond explains a 20-fold increase in affinity yet note that the mobility of the glycan moiety allows the hydrogen-bond interaction to occur. The hydrogen-bonding preferences and
Highly selective Diels–Alder and Heck arylation reactions in a divergent synthesis of isoindolo- and pyrrolo-fused polycyclic indoles from 2-formylpyrrole
Beilstein J. Org. Chem. 2020, 16, 1320–1334, doi:10.3762/bjoc.16.113
- endo selectivity in the Diels–Alder cycloadditions. Since experimental and theoretical results have demonstrated that the nature of the C–H···π interaction mainly depends on the dispersion interactions [64][67][77], these are probably not only at the origin of the endo stereoselectivity of the present
Understanding the role of active site residues in CotB2 catalysis using a cluster model
Beilstein J. Org. Chem. 2020, 16, 50–59, doi:10.3762/bjoc.16.7
- that maximized intramolecular dispersion interactions [45][46]. In the active site model of E, the carbocation at C6 had a greater distance from the pyrophosphate group than C2 in cation D (6.03 Å vs 5.03 Å) and likely contributed to a slight destabilizing effect in the active site model. This was in
A combinatorial approach to improving the performance of azoarene photoswitches
Beilstein J. Org. Chem. 2019, 15, 2753–2764, doi:10.3762/bjoc.15.266
- ). The analysis of the NCI surfaces indicates that inclusion of F atoms in the ortho-position promotes stabilizing dispersion interactions with the pyrazole ring, provoking a tilting of the heteroring from 92° in 4pzH to 118° in 4pzH-F1 and to 121° in 4pzH-F2 (Figure 4). Stabilizing F···pyrazole
An azobenzene container showing a definite folding – synthesis and structural investigation
Beilstein J. Org. Chem. 2019, 15, 1534–1544, doi:10.3762/bjoc.15.156
- potentials B3LYP [53][54][55] and B3LYP-D3 [56][57]. The latter includes an additional dispersion correction and describes dispersion interactions more accurately for larger atomic distances. As basis set 6-31G* [58][59] was applied. In the case of the cis,trans- and cis,cis-isomers we tried to calculate all
- amounts to only 1.9 kcal/mol. The reason for that is the high gain of attractive dispersion interactions due to the compact structure of the cis,cis-isomer. Therefore, we expected that the switching process from cis,trans-10 to cis,cis-10 is more easily realizable by an extern light stimulus than the
Adhesion, forces and the stability of interfaces
Beilstein J. Org. Chem. 2019, 15, 106–129, doi:10.3762/bjoc.15.12
- interactions were nearly exclusively attributed to electrostatic interactions. We discuss the importance of dispersion interactions for the stabilization in systems that are traditionally explained in terms of the “special interactions” mentioned above. System stabilization can be explained by using
- interactions, which are those between static multipoles in one and multipoles in the other molecule that are induced by charge shifts; 3) dispersion interactions, which are those between non-static multipoles in one molecule and induced multipoles in the other molecule; and 4) exchange repulsions or Pauli
- expansions by multicenter expansions are termed distributed multipole analysis, distributed polarizabilities, and distributed dispersion interaction [2]. The possibility of calculating electrostatic, induction and dispersion interactions by dividing molecules into subsystems, mostly atoms or atom groups
The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study
Beilstein J. Org. Chem. 2018, 14, 2872–2880, doi:10.3762/bjoc.14.266
- this class of catalysts [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44]. Since the M06 functional already includes some medium-range dispersion it is usually used without additional corrections to better describe dispersion interactions. The commonly used D3 semiempirical correction for
Dispersion-mediated steering of organic adsorbates on a precovered silicon surface
Beilstein J. Org. Chem. 2018, 14, 2715–2721, doi:10.3762/bjoc.14.249
- limiting factor regarding the packing of molecules. Here we show that the attractive part of the van der Waals potential can be similarly decisive. For the semiconductor surface Si(001), an already covalently bonded molecule of cyclooctyne steers a second incoming molecule via dispersion interactions onto
- proposed that the occupied sites might “steer” impinging molecules via an attractive adsorption potential close to an already adsorbed molecule [6]. Here, we will show that this steering potential is indeed found and is caused by attractive dispersion interactions. To this end, we investigated the
- negative bonding energies Ebond in case of the precovered surface. This is not found in the computation that omits dispersion forces (Figure 3b). Thus, dispersion interactions not only stabilize product 3 but act along the whole adsorption path of 1 onto Si(001). This leads us to a comprehensive
Evaluation of dispersion type metal···π arene interaction in arylbismuth compounds – an experimental and theoretical study
Beilstein J. Org. Chem. 2018, 14, 2125–2145, doi:10.3762/bjoc.14.187
- order to assess the role of dispersion interactions for the existence of structural features in compounds including Bi···π interactions, we focus our study on the wealth of structural information for BiPh3 (compound 1). Note that various structural motifs present in the polymorphs of compound 1 can be
- structures of 1–5 described above revealed the presence of London dispersion type interactions in the solid state, with bismuth acting as dispersion energy donor (DED) only in some cases. In the absence of strong donor acceptor type interactions a competition between the different types of dispersion
- interactions (Bi···π, π···π or C–H···π) is observed and thus leads to different structural features in the solid state (Table 1). Here the question arises how important and how large these interactions are and whether any type of interaction is dominating. For this reason computational studies have been
The phenyl vinyl ether–methanol complex: a model system for quantum chemistry benchmarking
Beilstein J. Org. Chem. 2018, 14, 1642–1654, doi:10.3762/bjoc.14.140
- electronically excited (S1) state is analyzed, in which a destabilization of the OH∙∙∙O structure compared to the S0 state is observed experimentally and theoretically. Keywords: dispersion interactions; IR spectroscopy; quantum-chemical calculations; rotational spectroscopy; structure determination; weak
- dispersion interactions [48]. The aim of the presented study is the unambiguous experimental identification of the preferred binding site of a first methanol solvent molecule to the multivalent hydrogen bond scaffold of phenyl vinyl ether, followed by a classification of theoretical methods in terms of
- (frozen-core approximation). Furthermore, we analyzed the relative impact of dispersion interactions in the different complexes through a local orbital analysis of the CCSD (connected) doubles energy terms. The latter discussion is complemented with dispersion interaction density (DID) plots [48]. The
London dispersion as important factor for the stabilization of (Z)-azobenzenes in the presence of hydrogen bonding
Beilstein J. Org. Chem. 2018, 14, 1238–1243, doi:10.3762/bjoc.14.106
- important classes of molecular switches is crucial for the design of light-responsive materials using this entity. Herein, we present the stabilization of metastable (Z)-azobenzenes by London dispersion interactions, even in the presence of comparably stronger hydrogen bonds in various solvents. The Z→E
- isomerization rates of several N-substituted 4,4′-bis(4-aminobenzyl)azobenzenes were measured. An intramolecular stabilization was observed and explained by the interplay of intramolecular amide and carbamate hydrogen bonds as well as London dispersion interactions. Whereas in toluene, 1,4-dioxane and tert
- -butyl methyl ether the hydrogen bonds dominate, the variation in stabilization of the different substituted azobenzenes in dimethyl sulfoxide can be rationalized by London dispersion interactions. These findings were supported by conformational analysis and DFT computations and reveal low-energy London
Are dispersion corrections accurate outside equilibrium? A case study on benzene
Beilstein J. Org. Chem. 2018, 14, 1181–1191, doi:10.3762/bjoc.14.99
- electronic interactions [34][35] and non-additive C9 or Axilrod-Teller-Muto (ATM) dispersion interactions here. The former cause large differences in the effective pairwise C6 and higher-order dispersion coefficients, relative to corresponding values for free atoms [33][37][38] (these are known as Type-B non
- with the benchmarks, thus indicating its ability to simultaneously capture competing energy contributions. All other methods are much more successful here than in the previous tests, reflecting their consistency in reproducing electrostatic effects compared to dispersion interactions which are more-or
Correlation effects and many-body interactions in water clusters
Beilstein J. Org. Chem. 2018, 14, 979–991, doi:10.3762/bjoc.14.83
- dispersion interactions are practically negligible for all studied sytems. The two-body dispersion interaction, however, plays a significant role in the formation of the structures of the water clusters and their stability, since it leads to a distinct compression of the cluster sizes compared to the
- minimum structures of the clusters. Dispersion interactions, however, make up a significant contribution of about 60% to the total interaction energies in larger water clusters and lead to a compression of the cluster sizes on average. The total magnitude of the electron correlation contribution to the
- interaction energy is, however, only about half the size of the sum of the two-, three- and four-body dispersion interactions, i.e., the large dispersion interaction contribution is strongly quenched by further repulsive correlation contributions. Noting that the correlation effect to the molecular dipole
Local energy decomposition analysis of hydrogen-bonded dimers within a domain-based pair natural orbital coupled cluster study
Beilstein J. Org. Chem. 2018, 14, 919–929, doi:10.3762/bjoc.14.79
- gratefully acknowledge the Priority Program “Control of Dispersion Interactions in Molecular Chemistry” (SPP 1807) of the Deutsche Forschungsgemeinschaft for financial support.
Terahertz spectroscopy of 2,4,6-trinitrotoluene molecular solids from first principles
Beilstein J. Org. Chem. 2018, 14, 381–388, doi:10.3762/bjoc.14.26
- theory that includes Tkatchenko–Scheffler pair-wise dispersion interactions. Furthermore, we show that for these polymorphs the theoretical results are only weakly affected by many-body dispersion contributions. The absence of dispersion interactions, however, causes sizable shifts in vibrational
- yield reliable simulated spectra for complex materials is density functional theory (DFT) [23]. A significant complication, however, is that conventionally used exchange–correlation energy functionals in DFT do not describe the intermolecular dispersion interactions well. Therefore, early calculations
- calculations reported in [46]. Here, however, this assignment is obtained from first principles. The effect of the pair-wise dispersion interactions on the vibrational modes themselves (i.e., beyond just a shift in their frequencies) can be assessed by considering the (absolute value of the) scalar product of
Experimental and theoretical insights in the alkene–arene intramolecular π-stacking interaction
Beilstein J. Org. Chem. 2016, 12, 1616–1623, doi:10.3762/bjoc.12.158
- the results presented herein, the extra stabilization of the CF3 substituted systems cannot be due to polar or charge-transfer effects but rather from dispersion interactions [27]. In an effort to prove this hypothesis, we performed an energy decomposition analysis (EDA) at the B3LYP-D3/TZ2P level
Aggregation behaviour of amphiphilic cyclodextrins: the nucleation stage by atomistic molecular dynamics simulations
Beilstein J. Org. Chem. 2015, 11, 2459–2473, doi:10.3762/bjoc.11.267
- molecules or by dispersion interactions at their lateral surface. We suggest that these aggregates can also form the nucleation stage of larger systems as well as the building blocks of micelles, vesicle, membranes, or generally nanoparticles thus opening new perspectives in the design of aggregates
- (see Table 2 and Supporting Information File 1, Figure S2). The case of Figure 7b has about the same stability, as said before, due to a different combination of dispersion interactions and hydrogen bonds. In this case, in fact, molecule D shows both self-inclusion of a P group and inclusion of another
- interaction of a third molecule (molecule B in Figure 8), interacting with the A and D molecules through dispersion interactions involving a few H groups of the B molecule and the P groups of the A molecule. An even looser interaction with these molecules is shown by the fourth one (molecule C in Figure 8
Other Beilstein-Institut Open Science Activities
